Antimicrobial coatings

ABSTRACT

The disclosure provides polymers having antimicrobial activity and articles with the polymers coated thereon. The polymers include a first pendant group comprising a first quaternary ammonium component, a second pendant group comprising a nonpolar component, and a third pendant group comprising an organosilane component. The disclosure also includes methods of coating articles with the antimicrobial polymers. The methods further include the use of adhesion-promoting reagents.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No.13/115,146, filed May 25, 2011, which claims the benefit of U.S.Provisional Patent Application Nos. 61/348,044 and 61/348,157, bothfiled on May 25, 2010, which are incorporated herein by reference intheir entirety.

BACKGROUND

Surfaces that are intended to be touched by human operators,accordingly, will be exposed to the microorganisms either typically orincidentally found on skin. Touch panels, for example, can be found inapplications from ATM's to casinos to point of sale terminals andportable computers. Since the data entry is based on contact, touchpanels are inherently susceptible to scratches and to microbialcontamination. Other surfaces that may be prone to contamination includecountertops, bedrails, writing utensils, and keypads, for example.

These surfaces provide a suitable home for bacteria, fungi, algae, andother one celled organisms which thrive and propagate based on theavailability of appropriate amounts of moisture, temperature, nutrients,and receptive surfaces. As these organisms metabolize, they producechemical by-products. These chemicals are known to damage (e.g., etch)certain surfaces (e.g., touch sensitive panels). Further, the biomass ofsuch colonies fog or obscure the optical properties of the surfaces,irreparably damaging them. Cleaning and disinfection with chemicalswhich leach and poison the organisms and environmental controls whichminimize moisture have, to date, been the response to this problem.Although cleaning and disinfection is common practice, it is done withthe knowledge of the risks of sub-lethal dose levels, ineffective doses,resistant organisms, environmental exposure, human exposure, and thelimited duration of such cleaners after the initial treatment.

Typical touch screen panels, e.g., capacitive touch screen panels,require direct contact with the skin of the user's finger. Thus, thesepanels are directly contacted by many different users. As theseorganisms thrive, the variety of chemicals that these organisms produceare also known to affect the human user. Thus, these microorganisms, aswell as their metabolic products can pose serious health risks to usersranging from minor skin irritation to more serious toxic response anddisease.

The foregoing concerns demonstrate growing detrimental effects ofmicroorganisms on computer touch panels and a need for controllingmicroorganisms that may be disposed on such touch sensitive panels. Theuse of environmental controls has limited effectiveness on microorganismprevention in part because of the wide variety of environmentalconditions under which various microorganisms can survive and in partbecause of the costs and difficulty of actually keeping moisture levelssufficiently low to minimize microbial growth.

There exists a need for simple means to prevent the colonization ofarticles by microorganisms and/or a means to reduce the number of livingmicroorganisms that become disposed on a surface.

SUMMARY

In view of the general need to control the number of viablemicroorganisms on a surface that is intentionally touched by its user,the present disclosure provides an antimicrobial polymer that can beused, in some embodiments, to form a coating that is bonded to atouch-sensitive surface. The antimicrobial polymer may include chemicalcomponents that impart other desirable properties (e.g., adhesiveproperties, scratch resistance properties, antistatic properties) forthe article on which it is applied. In some embodiments, the componentsof the polymer may be selected for their optically-transparentproperties.

Thus, in one aspect, the present disclosure provides an article. Thearticle can comprise a touch-sensitive substrate comprising a surface.The article further can comprise an organic polymer having a pluralityof pendant groups. The organic polymer can be coupled to the surface.The plurality of pendant groups can comprise a first pendant groupcomprising a first quaternary ammonium component. The plurality ofpendant groups further can comprise a second pendant group comprising anonpolar component. The plurality of pendant groups further can comprisea third pendant group comprising a first organosilane or organic silaneester component. In some embodiments, the article further can comprise asiliceous substrate that includes a first side and a second side. Inthese embodiments, the organic polymer can be coupled to the first sideof the siliceous substrate and the touch-sensitive substrate can becoupled to the second side of the siliceous substrate.

In any of the above embodiments, the article does not comprise aconductive layer.

In any of the above embodiments, the organic polymer further cancomprise a second quaternary ammonium component.

In any of the above embodiments, the organic polymer further cancomprise a second organosilane or organic silane ester component. In anyof the above embodiments, at least one of the pendant components cancomprise a fluorochemical.

In any of the above embodiments, in the organic polymer, the ratio ofthe number of N atoms associated with the first quaternary ammoniumcomponent and second quaternary ammonium component, if present, and thenumber of Si atoms associated with the first organosilane component andsecond organosilane component, if present, is about 0.1:1 to about 10:1.

In any of the above embodiments, the surface to which the organicpolymer is coupled can be a glass or a polymeric surface. In any of theabove embodiments, the siliceous substrate can be covalently coupled tothe touch-sensitive substrate.

In another aspect, the present disclosure provides a method of making acoated article. The method can comprise forming a first composition ofan organic polymer in a solvent. The polymer can have a plurality ofpendant groups comprising: a first pendant group that includes a firstquaternary ammonium component; a second pendant group that includes anonpolar component; and a third pendant group that includes anorganosilane or organic silane ester component. The method further cancomprise mixing a second quaternary ammonium component with the firstcomposition to form a first mixture. The method further can comprisecontacting the first mixture with a substrate under conditions suitableto form covalent linkages between the organic polymer, the substrate,and the second quaternary ammonium compound. In some embodiments, themethod further can comprise, after contacting the first mixture with thesubstrate, rinsing the coated article. In any of the above embodiments,the method further can comprise coupling the substrate to atouch-sensitive substrate. In any of the above embodiments, the methodfurther can comprise providing a second composition comprising anadhesion-promoting reagent in a solvent and contacting the secondcomposition with the substrate, wherein contacting the secondcomposition with the substrate occurs prior to contacting the firstmixture with the substrate.

In yet another aspect, the present disclosure provides a method ofmaking a coated article. The method can comprise forming a firstcomposition of an organic polymer in a solvent, mixing anadhesion-promoting reagent with the first composition to form a secondmixture, and contacting the second mixture with a siliceous substrateunder conditions suitable to form covalent linkages between organicpolymer and the siliceous substrate. The polymer can have a plurality ofpendant groups, including a first pendant group comprising a firstquaternary ammonium component, a second pendant group comprising anonpolar component, and a third pendant group comprising a firstorganosilane component. In any embodiment of the method, forming asecond mixture further can comprise mixing a second quaternary ammoniumcomponent with the adhesion-promoting reagent and the first composition.In any embodiment of the method, the adhesion-promoting reagent can beselected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane. In any embodiment, the method furthercan comprise providing a second composition comprising anadhesion-promoting reagent in organic solvent and contacting the secondcomposition with the substrate, wherein contacting the secondcomposition with the substrate occurs prior to contacting the secondmixture with the substrate.

In yet another aspect, the present disclosure provides a method ofmaking a coated article. The method can comprise forming a firstcomposition of an organic polymer in organic solvent. The polymer canhave a plurality of pendant groups comprising a first pendant group thatincludes a first quaternary ammonium component a second pendant groupthat includes a nonpolar component, and a third pendant group thatincludes an organosilane or organic silane ester component. The methodfurther can comprise mixing a second quaternary ammonium compound withthe first composition to form a first mixture. The method further cancomprise contacting the first mixture with a touch-sensitive substrateunder conditions suitable to form covalent linkages between organicpolymer and the touch-sensitive substrate. In some embodiments, themethod further can comprise, after contacting the first mixture with thetouch-sensitive substrate, rinsing the coated article. In any of theabove embodiments, the method further can comprise providing a secondcomposition comprising an adhesion-promoting reagent in organic solventand contacting the second composition with the touch-sensitivesubstrate, wherein contacting the second composition with thetouch-sensitive substrate occurs prior to contacting the first mixturewith the touch-sensitive substrate.

In yet another aspect, the present disclosure provides a method ofmaking a coated article. The method can comprise forming a firstcomposition of an organic polymer in organic solvent, mixing anadhesion-promoting reagent with the first composition to form a secondmixture, and contacting the second mixture with a touch-sensitivesubstrate under conditions suitable to form covalent linkages betweenorganic polymer and the touch-sensitive substrate. The polymer can havea plurality of pendant groups, including a first pendant groupcomprising a first quaternary ammonium component, a second pendant groupcomprising a nonpolar component, and a third pendant group comprising afirst organosilane component. In any embodiment of the method, forming asecond mixture further can comprise mixing a second quaternary ammoniumcomponent with the adhesion-promoting reagent and the first composition.In any embodiment of the method, the adhesion-promoting reagent can beselected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane. In any embodiment, the method furthercan comprise providing a second composition comprising anadhesion-promoting reagent in organic solvent and contacting the secondcomposition with the touch-sensitive substrate, wherein contacting thesecond composition with the touch-sensitive substrate occurs prior tocontacting the second mixture with the touch-sensitive substrate.

In yet another aspect, the present disclosure provides an antimicrobialpolymer composition. The composition can comprise an organic polymerhaving a plurality of pendant groups with the proviso that the polymerdoes not comprise a pendant group that includes a carboxylate oralkoxylate chemical group. The pendant groups can include a firstpendant group comprising a first quaternary ammonium component. Thependant groups further can include a second pendant group comprising aperfluorinated nonpolar component. The pendant groups further caninclude a third pendant group comprising a first organosilane component.In some embodiments, the antimicrobial composition further can include afourth pendant component, wherein the fourth pendant component comprisesa polar chemical group.

The words “preferred” and “preferably” refer to embodiments of theinvention that may afford certain benefits, under certain circumstances.However, other embodiments may also be preferred, under the same orother circumstances. Furthermore, the recitation of one or morepreferred embodiments does not imply that other embodiments are notuseful, and is not intended to exclude other embodiments from the scopeof the invention.

As used herein, “a,” “an,” “the,” “at least one,” and “one or more” areused interchangeably. Thus, for example, an article comprising “a”siliceous substrate can be interpreted to mean that the article caninclude “one or more” siliceous substrates.

The term “and/or” means one or all of the listed elements or acombination of any two or more of the listed elements.

Also herein, the recitations of numerical ranges by endpoints includeall numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.80, 4, 5, etc.).

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which examples can beused in various combinations. In each instance, the recited list servesonly as a representative group and should not be interpreted as anexclusive list.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be further explained with reference to the drawingfigures listed below, where like structure is referenced by likenumerals throughout the several views.

FIG. 1 a is a top perspective view of an embodiment of an antimicrobialtouch screen article, with a capacitive layer, according to the presentdisclosure.

FIG. 1 b is a top perspective view of an embodiment of an antimicrobialtouch screen article, without a capacitive layer, according to thepresent disclosure.

FIG. 2 is a top perspective view of another embodiment of anantimicrobial touch screen article according to the present disclosure.

FIG. 3 is a top perspective view of another embodiment of anantimicrobial touch screen article according to the present disclosure.

FIG. 4 is a block diagram of one embodiment of a method of making acoated article according to the present disclosure.

FIG. 5 is a bar graph showing the log reduction of Staphylococcus aureusbacteria according to one test method after exposure to severalembodiments of an article comprising an antimicrobial polymer of thepresent disclosure.

DETAILED DESCRIPTION

Polymeric materials are provided that can contain a plurality ofdifferent pendant groups. Methods of making the polymeric material andcompositions that contain the polymeric material are also provided.Additionally, articles with coatings that contain the polymeric materialare provided. The polymeric material in the coatings is oftencrosslinked. The coatings can be antimicrobial, scratch-resistant, orboth.

Before any embodiments of the invention are explained in detail, it isto be understood that the invention is not limited in its application tothe details of construction and the arrangement of components set forthin the following description or illustrated in the accompanyingdrawings. The invention is capable of other embodiments and of beingpracticed or of being carried out in various ways. Also, it is to beunderstood that the phraseology and terminology used herein is for thepurpose of description and should not be regarded as limiting. The useof “including,” “comprising,” “containing,” or “having” and variationsthereof herein is meant to encompass the items listed thereafter andequivalents thereof as well as additional items. Unless specified orlimited otherwise, the terms “supported,” and “coupled” and variationsthereof are used broadly and encompass both direct and indirect supportsand couplings. It is to be understood that other embodiments may beutilized and structural or logical changes may be made without departingfrom the scope of the present disclosure. Furthermore, terms such as“front,” “rear,” “top,” “bottom,” and the like are only used to describeelements as they relate to one another, but are in no way meant torecite specific orientations of the apparatus, to indicate or implynecessary or required orientations of the apparatus, or to specify howthe invention described herein will be used, mounted, displayed, orpositioned in use.

The term “antimicrobial” refers to material that kills microorganisms orinhibits their growth.

The term “silane” refers to a compound having four groups attached to asilicon atom. That is, the silane has a silicon-containing group.

The term “alkoxysilyl” refers to a silicon-containing group having analkoxy group bonded directly to the silicon atom. The alkoxysilyl canbe, for example, of formula —Si(OR)(Rx)₂ where R is an alkyl and each Rxis independently a hydroxyl, alkoxy, alkyl, perfluoroalkyl, aryl,aralkyl, or part of a silicone.

The term “ester equivalent” means groups such as silane amides (RNR′Si),silane alkanoates (RC(O)OSi), Si—O—Si, SiN(R)—Si, SiSR and RCONR′Si thatare thermally and/or catalytically displaceable by R″OH. R and R′ areindependently chosen and can include hydrogen, alkyl, arylalkyl,alkenyl, alkynyl, cycloalkyl, and substituted analogs such asalkoxyalkyl, aminoalkyl, and alkylaminoalkyl. R″ may be the same as Rand R′ except it may not be H.

The term “hydroxysilyl” refers to a silicon-containing group having ahydroxyl group bonded directly to the silicon atom. The hydroxysilyl canbe, for example, of formula —Si(OH)(Rx)₂ where Rx is an alkyl,perfluoralkyl, aryl, aralkyl, alkoxy, hydroxyl, or part of a silicone. Acompound having a hydroxysilyl group is often referred to as a“silanol”. Silanols are a subset of silanes.

The term “silicone” refers to a moiety that contains asilicon-oxygen-silicon linkage group. Any other suitable groups can beattached to the silicon atoms. Such a linkage can result from thereaction of a first silane (e.g., a first silicon-containing group suchas a first alkoxysilyl group or hydroxysilyl group) with a second silane(e.g., a second silicon-containing group such as a second alkoxysilylgroup or hydroxysilyl group). In some embodiments, the silicone is partof a “silicone network”. A silicone network results when a first silane(i.e., a first silicon-containing group) reacts with a second silane(e.g., a second silicon-containing group) plus a third silane (e.g., athird silicon-containing group such as a third alkoxysilyl group orhydroxysilyl group) or when a first silane (e.g., a firstsilicon-containing group) reacts with a second silane (e.g., a secondsilicon-containing group) plus a third silane (e.g., a thirdsilicon-containing group) and a fourth silane (e.g., a fourthsilicon-containing group such as a fourth alkoxysilyl group orhydroxysilyl group).

As used herein, the phrases “polymeric material with a plurality ofpendant groups”, “polymeric material with multiple pendant groups”, orsimilar phrases are used interchangeably to refer to a polymericmaterial that has at least three different types of pendant groups. Themultiple pendant groups include (1) a first pendant group containing aquaternary amino group; (2) a second pendant group containing a nonpolargroup; and (3) a third pendant group having an organosilane group. Thepolymeric material with multiple pendant groups can be crosslinkedthrough a condensation reaction of multiple organosilane groups.Furthermore, the polymeric material can be covalently coupled to asurface comprising a silanol group or, preferably, a plurality ofsilanol groups.

The present disclosure is generally directed to articles comprising anantimicrobial coating and methods of making said articles comprising anantimicrobial coating. The articles further comprise a substrate. Insome embodiments, the substrate comprises a touch-sensitive substrate(e.g., a computer display touch panel). The touch-sensitive substratemay comprise an active portion. The active portion of the substrateincludes a surface configured to be touched (e.g., by a finger, astylus, or the like). “Active portion” is used herein in the broadestsense and refers to a region of the substrate that can transduce atactile stimulus into an electrical signal. Nonlimiting examples ofdevices that comprise a substrate with an “active portion” include touchscreens (e.g., computer touch screens, personal digital assistant touchscreens, telephone touch screens, card reader touch screens, casinogaming devices, touch-enabled industrial equipment controls,touch-enabled vehicle accessory controls, and the like) Exemplary touchscreens are disclosed in U.S. Pat. Nos. 6,504,582; 6,504,583; 7,157,649;and U.S. Patent Application Publication No. 2005/0259378.

Turning to the Figures, FIG. 1 a shows one embodiment of anantimicrobial touch sensor 110 according to the present invention. Thetouch sensor 110 may be a touch sensitive panel such as, for example, a“surface capacitive” computer touch panel, available from 3M TouchSystems, Methuen, Mass., made up of several different layers. The touchsensor 110 features an antimicrobial touch panel 112.

Touch panel 112 includes electrically insulative substrate 114.Insulative substrate 114 may be constructed from glass, plastic oranother transparent medium, for example. The touch panel 112 furthercomprises a touch-sensitive active portion 115 on the insulativesubstrate 114. Active portion 115 includes a transparent, electricallyconductive layer 116 deposited directly on substrate 114. Conductivelayer 116, for example, can be a tin oxide layer having a thickness oftwenty to sixty nanometers and may be deposited by sputtering, vacuumdeposition and other techniques known in the art. The thickness of thelayers is exaggerated in FIG. 1 a for illustrative purposes only and isnot intended to represent the layers to scale. Conductive layer 116 mayalso include a conductive polymeric material or a conductiveorganic-inorganic composite.

A conductive pattern, not shown, can be disposed about the perimeter ofconductive layer 116 to provide a uniform electric field throughout thelayer 116 in order to establish the point of contact between the panel112 and a finger or stylus.

Active portion 115 may also include protective layer 118 deposited overconductive layer 116 to provide abrasion resistance to protectconductive layer 116. Protective layer 118 may be a layer of anorganosiloxane formed by applying to the article a composition (e.g., asolution) comprising methyltriethoxysilane, tetraethylorthosilicate,isopropanol and water. Additionally, or alternatively, the protectivelayer may comprise a hardcoat material (e.g., the glare-resistanthardcoat described in Example 1 of U.S. Pat. No. 7,294,405).

Second conductive layer 120 may be provided to shield touch sensor 110from noise which may result from the electric circuits of a displayunit, not shown, to which display 110 may be attached and may similarlyinclude a tin oxide layer deposited in a similar manner as discussedwith reference to conductive layer 116. However, conductive layer 120 isnot a necessary limitation of the invention as touch sensor 110 canfunction without it.

Antimicrobial polymer layer 122 in accordance with this disclosure iscoupled to active portion 115, usually on protective layer 118 or evendirectly to conductive layer 116 if protective layer 118 is not presentor to the outermost layer, if additional layers (not shown) are presentto reduce energy dissipation of an object contacting touch sensor 110.In this configuration, antimicrobial polymer layer 122 can minimize orprevent damage to touch sensor 110, providing an easy glide experienceto the touch screen user, as well as inhibit the survival and growth ofmicroorganisms which come to rest on touch sensor 110.

FIG. 1 b shows one embodiment of another antimicrobial touch sensor 110according to the present invention. The touch sensor 110 may be a touchsensitive panel such as, for example, a “projected capacitive” computertouch panel in a projected capacitive touch screen, made up of severaldifferent layers. The touch sensor 110 features an antimicrobial touchpanel 112.

Touch panel 112 includes electrically insulative substrate 114.Insulative substrate 114 may be constructed from glass, plastic oranother transparent medium, for example.

A conductive layer 124 can be disposed beneath the substrate 114 inorder to establish the point of contact between the panel 112 and afinger or stylus. In some embodiments (not shown), conductive layer 124may be a plurality of conductive layers (e.g. arrays of electrodes) withdielectric layers disposed there between. Touch sensors with thisconfiguration are disclosed in U.S. Pat. No. 8,411,066.

Touch panel 112 may also include protective layer 118 deposited overinsulative substrate 114 to provide abrasion resistance to protectinsulative substrate 114. Protective layer 118 may be a layer of anorganosiloxane formed by applying to the article a composition (e.g., asolution) comprising methyltriethoxysilane, tetraethylorthosilicate,isopropanol and water. Additionally, or alternatively, the protectivelayer may comprise a hardcoat material (e.g., the glare-resistanthardcoat described in Example 1 of U.S. Pat. No. 7,294,405).

Antimicrobial polymer layer 122 in accordance with this disclosure iscoupled to protective layer 118 or even directly to insulative substrate114 if protective layer 118 is not present or to the outermost layer, ifadditional layers (not shown) are present to reduce energy dissipationof an object contacting touch sensor 110. In this configuration,antimicrobial polymer layer 122 can minimize or prevent damage to touchsensor 110, providing an easy glide experience to the touch screen user,as well as inhibit the survival and growth of microorganisms which cometo rest on touch sensor 110.

FIG. 2 shows another embodiment of a touch sensor 210. The touch sensor210 may include, for example, a resistive computer touch panel 212,available from Elo TouchSystems, Freemont, Calif., which includesinsulative substrate 214 and conductive layer 216, similar to FIG. 1 a.Protective layer 218 may include a hard coating which protects andsupports deformable conductive layer 224 interposed between conductivelayer 216 and protective layer 218. A nonlimiting example of a suitablehard coating includes the glare-resistant hardcoat described in Example1 of U.S. Pat. No. 7,294,405. As touch sensor 210 is contacted by afinger or stylus deformable conductive layer 224 compresses and makescontact with conductive layer 216 to indicate the position of thecontact. Antimicrobial polymer layer 222 is applied to protective layer218.

FIG. 3 shows one embodiment of a vibration-sensing touch sensor 350 thatincludes a rectangular touch plate 370 and vibration sensors 360, 362,364, and 366 located at the corners and coupled to the touch plate. Whenintegrated into a system, for example overlaying an electronic display,the border portion 375 of touch sensor 350 may be covered by a bezel,leaving an intended touch area 380 exposed to a user. Dashed line 390 isused to indicate a separation between the border area 375 and theintended touch area 380. Dashed line 390 is an arbitrary designator, anddoes not necessarily indicate that touches outside of its inscribed areacannot be detected. To the contrary, dashed line 390 merely inscribes anarea where touch inputs are intended or expected to occur, which mayinclude the entire touch plate or some portion or portions thereof. Whendashed lines are used in this document to designate intended touchareas, they are used in this manner. Antimicrobial polymers (not shown)of the present disclosure can be applied directly or indirectly to thesurface of the touch area 380 of the vibration-sensing touch sensor 350.An example of indirect application includes applying the antimicrobialpolymer to one side of a polymer film and a pressure-sensitive adhesiveto the other side of the film; then applying the adhesive side of thefilm to the touch area of the vibration-sensing touch sensor.

While the touch plate is shown as rectangular in FIG. 3, it can be ofany arbitrary shape. The touch plate can be glass, acrylic,polycarbonate, metal, wood, or any other material cable of propagatingvibrations that can be caused or altered by a touch input to the touchplate and that can be sensed by the vibration sensors. To detect thetouch position in two dimensions on the touch plate, at least threevibrations sensors can be used, and are generally located at peripheralportions of the touch plate, although other locations can be used. Forconvenience, redundancy, or other reasons, it may be desirable to use atleast four vibration sensors, for example one at each corner of arectangular touch plate, as shown in FIG. 3. The vibration sensors canbe any sensors capable of detecting vibrations in the touch plate thatare caused or affected by a touch, for example bending wave vibrations.

Piezoelectric materials may provide exemplary vibrations sensors. Thevibration sensors can be mechanically coupled to the touch plate by useof an adhesive, solder, or other suitable material. Conductive traces orwires (not shown) can be connected to each of the vibration sensors forcommunication with controller electronics (not shown). Exemplaryvibration-sensing touch sensors, their operation, their components, andtheir layout on a sensor are disclosed in co-assigned U.S. PatentApplication Publication No. 2004/0233174 and U.S. Patent ApplicationPublication No. 2005/0134574.

Antimicrobial Polymers:

The present disclosure provides antimicrobial polymers. Theantimicrobial polymers are formed by reacting, in suitable organicsolvent, monomers that comprise a chemical group that serves one or morefunctional purposes in the polymer.

In some embodiments, the antimicrobial polymers can be coated (e.g., asa film or layer) onto a substrate as described herein. The polymers haveantimicrobial activity that can kill or inhibit microorganisms that comeinto contact with the polymer (e.g., on the surface of a touch panel).The antimicrobial activity can be tested using a standardizedantimicrobial resistance test such as, for example, JIS-Z 2801 (JapaneseIndustrial Standards; Japanese Standards Association; Tokyo, Japan). Thepolymers further have scratch-resistant properties. Thescratch-resistant property of the polymer can be tested using the ASTMtest method D 7027.26676.

Polymers of the present disclosure are formed in any suitable solvent(e.g., an organic solvent) that will solubilize or make a dispersion ofthe resultant polymer. Suitable organic solvents have a boiling pointabout 200° C. or lower and can be mixed with small portions (<10%, w/w)of acidified water without substantially degrading the solventproperties. Adding the acidified water to the solvent facilitatescomplete hydrolysis of silane groups which, in turn optimizes theformation of —Si—O—Si— bonds within the polymer and between the polymerand the substrate. This can result in improved durability ofantimicrobial coating on the substrate. Preferably, the solventflashpoint is 100° C. or lower. Nonlimiting examples of suitable organicsolvents include an alcohol (e.g., isopropyl alcohol, methanol), MEK,acetone, DMF, DMAC (dimethyl acetamide) ethyl acetate, THF, etc. Themonomers are mixed with the solvent and reacted to form an antimicrobialpolymer. Suitable monomers include derivatives of acrylate monomers,methacrylate monomers, vinyl monomers, and olefinic monomers. Themonomers comprise chemical groups that are pendant from the polymerafter the polymerization reaction. The pendant groups include a firstquaternary ammonium group, a nonpolar group, and a first organosilanegroup (e.g., trimethoxysilylpropane).

The polymer shown in Structure (I) shows a representation of a portionof an antimicrobial polymer made from acrylate or olefinic monomersaccording to the present disclosure.

Polymers of the present disclosure include pendant groups withantimicrobial activity. The groups with antimicrobial activity can beselected for properties that are desirable in the articles on which thepolymer is coated. For example, the antimicrobial group can be selectedbecause it provides a polymer having substantial optical clarity (i.e.high optical transmission throughout a narrow or broad spectrum ofwavelengths, low haze). These properties easily can be measured by aperson of ordinary skill in the art, for example, by methods disclosedherein. In the exemplary polymer of Structure (I), the first quaternaryammonium pendant group includes the quaternary ammonium moiety R³ andcan be derived from a monomer where:

-   -   R¹=H or CH₃,    -   R²═COO, CO, C₁-C₁₂ alkyl, aryl    -   R³=a quaternary ammonium having the formula        —(CH₂)_(n)—N(R⁷)(R⁸)(R⁹)(X⁻) where        -   n=1-3 (i.e., an alkyl group from C₁-C₃)        -   R⁷, R⁸, and R⁹ are independently an alkyl (C₁-C₂₂), aryl, or            a combination of chemical groups forming a ring structure;            and        -   X=Cl, Br, N(SO₂CF₃)₂, BF₄, OSO₂C₄F₉, OSO₂CF₃, OSO₃CH₃.

The first quaternary ammonium pendant groups are coupled (e.g.,covalently coupled) to the polymer such that, the antibiotic activity ofthe antimicrobial coupled to the polymer is insoluble in water (i.e.,the antimicrobial is non-leaching when the polymer is contacted with anaqueous solution). Nonlimiting examples of suitable antimicrobialquaternary ammonium components include the hexadecyldimethylethylamine,octadecyldimethylethylamine, hexadecyldimethylpropylamine andoctadecyldimethylpropylamine.

In the exemplary polymer of Structure (I), the nonpolar pendant groupincludes the nonpolar moiety R⁴ and can be derived from a monomer whereR⁴ is an unsubstituted or substituted alkyl group (C₄ to C₂₂), an arylgroup, perfluoroalkyl sulfonamide, perfluoroalkyl sulfone,perfluoroalkyl carboxamide, a class of free-radically reactivefluoroalkyl or fluoroalkylene group-containing compatibilizers of therespective chemical formulas: R_(ff)Q₃(X₁)_(n1) and(X₁)_(n1)Q₃R_(ff2)Q₃(X₁)_(n1)), where R_(ff) is a fluoroalkyl, R_(ff2)is a fluoroalkylene, Q₃ is a connecting group of valency at least 2 andis selected from the group consisting of a covalent bond, an alkylene,an arylene, an aralkylene, an alkarylene group, a straight or branchedchain or cycle-containing connecting group optionally containingheteroatoms such as O, N, and S and optionally a heteroatom-containingfunctional group such as carbonyl or sulfonyl, and combinations thereof;X₁ is a free-radically reactive group selected from (meth)acryl, —SH,allyl, or vinyl groups and n1 is independently 1 to 3. Typical Q₃ groupsinclude: —SO₂N(R)CH₂CH₂—; —SO₂N(CH₂CH₂)₂—; —(CH₂)_(m)—; —CH₂—O—(CH₂)₃—;and —C(O)NRCH₂CH₂—, where R is H or lower alkyl of 1 to 4 carbon atomsand m is 1 to 6. Preferably the fluoroalkyl or fluoroalkylene group is aperfluoroalkyl or perfluoroalkylene group. Exemplary, non-limitingperfluorobutyl-substituted acrylate compatibilizers meeting thesecriteria and useful in the present invention include one or more ofC₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂, C₄F₉SO₂N(CH₂CH₂OC(O)CH═CH₂)₂, orC₄F₉SO₂N(CH₃)CH₂CH₂OC(O)C(CH₃)═CH₂. One non-limiting example of apreferred fluoroalkyl-substituted monomers that may be utilized in thecomposition of the coat layer is: (1H,1H,2H,2H)-perfluorodecyl acrylate,available from Lancaster Synthesis of Windham, N.H. Numerous other(meth)acryl compounds with perfluoroalkyl moieties that may also beutilized in the composition of the coat layer are mentioned in U.S. Pat.No. 4,968,116, to Hulme-Lowe et al., and in U.S. Pat. No. 5,239,026(including perfluorocyclohexylmethyl methacrylate), to Babirad et al.Other fluorochemical (meth)acrylates that meet these criteria and may beutilized include, for example, 2,2,3,3,4,4,5,5-octafluorohexanedioldiacrylate and ω-hydro 2,2,3,3,4,4,5,5-octafluoropentyl acrylate(H—C₄F₈—CH₂O—C(O)—CH═CH₂). Other fluorochemical (meth)acrylates that maybe used alone, or as mixtures, are described in U.S. Pat. No. 6,238,798,to Kang et al.

Another monomer that may be used is a fluoroalkyl- orfluoroalkylene-substituted thiol or polythiol. Non-limiting examples ofthis type of monomers includes one or more of the following:C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂SH, C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂CH₂SH,C₄F₉SO₂N(CH₃)CH₂CH₂SH, and C₄F₉SO₂N(CH₃)CH(OC(O)CH₂SH)CH₂OC(O)CH₂SH.

In another preferred embodiment, the coating composition adds one ormore multi-olefinic compounds bearing at least one monovalentpoly(hexafluoropropylene oxide) (HFPO) moiety and optionally acompatibilizer such as a fluoroalkyl- or fluoroalkylene-substituted monoor multi-acrylate such as C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂,C₄F₉SO₂N(CH₂CH₂OC(O)CH═CH₂)₂, or C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)C(CH₃)═CH₂,alcohol, olefin, thiol or polythiol to fluoropolymer curing composition.Non-limiting examples of thiol or polythiol type of compatibilizerincludes one or more of the following: C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂SH,C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂CH₂SH, C₄F₉SO₂N(CH₃)CH₂CH₂SH, andC₄F₉SO₂N(CH₃)CH(OC(O)CH₂SH)CH₂OC(O)CH₂SH.

As used in the examples, unless otherwise noted, “HFPO—” refers to theend group F(CF(CF₃)CF₂O)_(a)CF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃, wherein “a” averages about 6.8, andthe methyl ester has an average molecular weight of 1,211 g/mol, andwhich can be prepared according to the method reported in U.S. Pat. No.3,250,808 (Moore et al.) with purification by fractional distillation.

The mono- or multi-olefinic compound bearing at least one monovalentpoly(hexafluoropropylene oxide) (HFPO) moiety preferably is in the formof a multiacrylate. These materials are of the formula: R_(fpe)Q(X)_(n)wherein Rfpe is the residue of a monovalent HFPO moiety, Q is aconnecting group comprising an alkylene, arylene, arylene-alkylene, oralkylene-arylene group and may comprise a straight or branched chainconnecting group which may contain heteroatoms such as O, N, and S, X isa free-radically reactive group selected from meth(acryl), allyl, orvinyl groups and n is 2 to 3. Typical Q group include: —(CH₂)_(m)—;—CH₂O(CH₂)₃—; and —C(O)NRCH₂CH₂—, where R is H or lower alkyl of 1 to 4carbon atoms and m is 1 to 6.

One class of multi-(meth)acryl compound bearing at least one monovalentpoly(hexafluoropropylene oxide) (HFPO) moiety comprises compoundsdescribed in International Publication WO 2005/113641.

Other mono- and multi-(meth)acryl compounds bearing at least onemonovalent poly(hexafluoropropylene oxide) (HFPO) moiety comprisecompounds which are Michael adducts of HFPO amine derivatives withmultiacrylates described in International Publication WO 2005/113642.

The nonpolar pendant group is a chemical group that increases therelative hydrophobicity of the antimicrobial polymer. The nonpolarpendant groups are selected for their ability to influence the surfaceenergy of the polymer. In particular, the nonpolar pendant groups areselected to impart a low surface energy polymer. Nonpolar pendant groupscan also increase the scratch resistance of the polymer, when thepolymer is coated onto a hard surface (e.g., glass). Nonlimiting exampleof suitable nonpolar groups include linear or branched alkanes (e.g.,isooctane, isobutane) and aromatic groups.

In the exemplary polymer of Structure (I), the first organosilanependant group includes the siloxane moiety R⁵ and can be derived from amonomer where:

-   -   R⁵═(CH₂)m—Si(OR¹⁰)₃,    -   m=1-6 (i.e., an alkyl group from C₁-C₆) and        -   R¹⁰=an alkyl group from C₁-C₃.

The first organosilane pendant group includes a silicon-containinggroup. This pendant group can crosslink the antimicrobial polymericmaterial, bond the antimicrobial polymeric material to a substrate, bonda second organosilane to the antimicrobial polymer, or it can confer theability of the polymer to perform any combination of the foregoingbonding configurations. A nonlimiting example of a suitable organosilanependant group is the propyl trimethoxysilane group found inmethacryloylpropyl trimethoxysilane.

Although Structure (I) shows a portion of an exemplary antimicrobialpolymer comprising three sequential monomers with different pendantgroups, it will be recognized that the antimicrobial polymer of thepresent disclosure is a random copolymer, with the number and order ofmonomeric subunits (a, b, c, and, optionally, d) influenced by therespective ratios of monomeric units in the polymerization reactionand/or the polymerization reaction conditions.

Antimicrobial polymers of the present disclosure optionally can include,in addition to the quaternary ammonium, nonpolar, and organosilanependant groups, a fourth pendant group that includes a polar component.The polar pendant group can confer adhesive properties that allow theantimicrobial polymer to adhere to certain substrates. Because the polarpendant groups promote adhesion of the antimicrobial polymer to thesubstrate, advantageously, this can result in an improved durability ofthe polymer on the substrate. In some embodiments, the polar pendantgroup may enhance the antimicrobial activity of the polymer. Suitablepolar pendant groups include, for example, N-hydroxymethylacrylamide,dimethylacrylamide, and alcohol groups.

In some embodiments, the antimicrobial polymer of the present disclosuredoes not comprise a pendant group that includes a carboxylate oralkoxylate chemical group.

Antimicrobial polymers of the present disclosure can be synthesized byreacting, in an organic solvent, monomers comprising the pendant groups.Suitable monomers for the reaction include, for example, acrylatemonomers, methacrylate monomers, and combinations thereof. Othersuitable monomers for the reaction include vinyl monomers and olefinicmonomers.

The monomers can be combined, on a weight percent basis, in variousratios in the reaction. In some embodiments, the monomer comprising thequaternary ammonium pendant group can comprise from about 20% to about80% of the monomers reacted to form a polymer. In some embodiments, themonomer comprising the quaternary ammonium pendant group can comprisegreater than 20% of the monomers reacted to form a polymer. In someembodiments, the monomer comprising the quaternary ammonium pendantgroup can comprise greater than 30% of the monomers reacted to form apolymer. In some embodiments, the monomer comprising the quaternaryammonium pendant group can comprise greater than 40% of the monomersreacted to form a polymer. In some embodiments, the monomer comprisingthe quaternary ammonium pendant group can comprise greater than 50% ofthe monomers reacted to form a polymer. In some embodiments, the monomercomprising the quaternary ammonium pendant group can comprise greaterthan 60% of the monomers reacted to form a polymer. In some embodiments,the monomer comprising the quaternary ammonium pendant group cancomprise greater than 70% of the monomers reacted to form a polymer. Insome embodiments, the monomer comprising the quaternary ammonium pendantgroup can comprise 70% to 80% of the monomers reacted to form a polymer.

In some embodiments, the monomer comprising the nonpolar pendant groupcan comprise from about 20% to about 60% of the monomers reacted to forma polymer. In some embodiments, the monomer comprising the quaternaryammonium pendant group can comprise greater than 20% of the monomersreacted to form a polymer. In some embodiments, the monomer comprisingthe quaternary ammonium pendant group can comprise greater than 30% ofthe monomers reacted to form a polymer. In some embodiments, the monomercomprising the quaternary ammonium pendant group can comprise 30% to 40%of the monomers reacted to form a polymer.

In some embodiments, the monomer comprising the organosilane pendantgroup can comprise from about 1% to about 20% of the monomers reacted toform a polymer. In some embodiments, the monomer comprising thequaternary ammonium pendant group can comprise greater than 2% of themonomers reacted to form a polymer. In some embodiments, the monomercomprising the quaternary ammonium pendant group can comprise greaterthan 5% of the monomers reacted to form a polymer. In some embodiments,the monomer comprising the quaternary ammonium pendant group cancomprise greater than 10% of the monomers reacted to form a polymer. Insome embodiments, the monomer comprising the quaternary ammonium pendantgroup can comprise greater than 15% of the monomers reacted to form apolymer. In some embodiments, the monomer comprising the quaternaryammonium pendant group can comprise 15% to 20% of the monomers reactedto form a polymer.

In some embodiments, the reaction mixture used to make the antimicrobialpolymer comprises at least 20% monomers comprising a quaternary ammoniumpendant group, at least 20% monomers comprising a nonpolar pendantgroup, and at least 2% monomers comprising an organosilane pendantgroup.

The monomers are mixed in an organic solvent and are reacted underconditions suitable to form a polymer. For example, the reaction mixturecan be purged with nitrogen to remove other dissolved gasses. In someembodiments, the reaction mixture can be sealed, heated, and mixed(e.g., mixed at 65° C.) for a period of time sufficient to allowpolymerization of, for example, at least 99.5% of the monomers. In someembodiments, an additional initiator (e.g.,2,2-Azobis(2-methylbutyronitrile), available from DuPont of Wilmington,Del., USA, under the trade name Vazo-67) can be added to the mixture toreact with any unreacted monomers from the original mixture. The extentof the reaction of monomers can be determined by, for example, acalculation of the percent solids in the mixture. The antimicrobialpolymer typically comprises about 25 weight percent (wt %) of thesolution in which it is made.

Adhesion-Promoting Reagents:

In any embodiment the method of making an antimicrobial coatingaccording the present disclosure, one or more adhesion-promoting reagentcan be used in the process. Suitable adhesion-promoting reagents includeorganosilane compounds having a silane group that can react to formSi—O—Si linkages and a leaving group (e.g. an alkoxy group).

The adhesion-promoting reagent can form Si—O—Si linkages with anotherorganosilane compound (e.g., an unreacted organosilane compound of thepresent disclosure), an organosilane-containing polymer (e.g., theantimicrobial polymers of the present disclosure), and/or a siliceoussubstrate (e.g., glass). Advantageously, the adhesion-promoting reagentspromote improved adhesion of the antimicrobial coatings by increasingthe number of attachment points (to the substrate) per antimicrobialmolecule. Furthermore, the adhesion-promoting reagents promote improveddurability of the antimicrobial coatings by increasing the number ofintramolecular linkages per antimicrobial polymer molecule and/or thenumber of linkages between the antimicrobial polymer and the substrate.

In addition to promoting the formation of Si—O—Si bonds between theorganosilane compounds in the coating compositions of the presentdisclosure, the preferred adhesion-promoting reagents can also be usedas an adhesion promoter to increase the interfacial adhesion between thesubstrate and the antimicrobial polymer composition of the presentdisclosure.

Nonlimiting examples of suitable adhesion-promoting reagents includeN-2(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine, andN-phenyl-3-aminopropyltrimethoxysilane. In view of the presentdisclosure, other suitable adhesion-promoting reagents will be apparentto a person having ordinary skill in the art.

Other suitable adhesion-promoting reagents are disclosed in U.S. PatentApplication Publication No. US 2008/0064825. For example,amino-substituted organosilane esters (e.g., alkoxy silanes) arepreferred adhesion-promoting reagents. The antimicrobial articles of thepresent disclosure may be made by reacting an amino-substitutedorganosilane ester or ester equivalent and an antimicrobial polymer thathas a plurality of polar functionalities combinatively reactive with thesilane ester or ester equivalent. The amino-substituted organosilaneester or ester equivalent bears on the silicon atom at least one esteror ester equivalent group, preferably 2, or more preferably 3 groups.Ester equivalents are well known to those skilled in the art and includecompounds such as silane amides (RNR′Si), silane alkanoates (RC(O)OSi),Si—O—Si, SiN(R)—Si, SiSR and RCONR′Si. These ester equivalents may alsobe cyclic such as those derived from ethylene glycol, ethanolamine,ethylenediamine and their amides. R and R′ are defined as in the “esterequivalent” definition herein.

3-aminopropyl alkoxysilanes are well known to cyclize on heating andthese RNHSi compounds would be useful in this invention. Preferably, theamino-substituted organosilane ester or ester equivalent has estergroups such as methoxy that are easily volatilized as methanol so as toavoid leaving residue at the interface which may interfere with bonding.The amino-substituted organosilane must have at least one esterequivalent; for example, it may be a trialkoxysilane.

For example, the amino-substituted organosilane may have the formula:ZNH-L-SiX′X″X′″, where Z is hydrogen, alkyl, or substituted alkylincluding amino-substituted alkyl; where L is a divalent straight chainC1-12 alkylene or may comprise a C3-8 cycloalkylene, 3-8 membered ringheterocycloalkylene, C2-12 alkenylene, C4-8 cycloalkenylene, 3-8membered ring heterocycloalkenylene or heteroarylene unit. L may beinterrupted by one or more divalent aromatic groups or heteroatomicgroups. The aromatic group may include a heteroaromatic. The heteroatomis preferably nitrogen, sulfur or oxygen. L is optionally substitutedwith C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, amino, C3-6cycloalkyl, 3-6 membered heterocycloalkyl, monocyclic aryl, 5-6 memberedring heteroaryl, C1-4 alkylcarbonyloxy, C1-4 alkyloxycarbonyl, C1-4alkylcarbonyl, formyl, C1-4 alkylcarbonylamino, or C1-4 aminocarbonyl. Lis further optionally interrupted by —O—, —S—, —N(Rc)-, —N(Rc)-C(O)—,—N(Rc)—C(O)—O—, —O—C(O)—N(Rc)-, —N(Rc)—C(O)—N(Rd)-, —O—C(O)—, —C(O)—O—,or —O—C(O)—O—. Each of Rc and Rd, independently, is hydrogen, alkyl,alkenyl, alkynyl, alkoxyalkyl, aminoalkyl (primary, secondary ortertiary), or haloalkyl; and each of X′, X″ and X′″ is a C1-18 alkyl,halogen, C1-8 alkoxy, C1-8 alkylcarbonyloxy, or amino group, with theproviso that at least one of X′, X″, and X′″ is a labile group. Further,any two or all of X′, X″ and X′″ may be joined through a covalent bond.The amino group may be an alkylamino group. Examples ofamino-substituted organosilanes include3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane (SILQUEST A-1110),3-aminopropyltriethoxysilane (SILQUEST A-1100),3-(2-aminoethyl)aminopropyltrimethoxysilane (SILQUEST A-1120), SILQUESTA-1130, (aminoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (SILQ UEST A-2120),bis-(γ-triethoxysilylpropyl)amine (SILQUEST A-1170),N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, oligomericaminosilanes such as DYNASYLAN 1146,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.

Additional “precursor” compounds such as a bis-silyl urea[RO)₃Si(CH₂)NR]₂C═O are also examples of amino-substituted organosilaneester or ester equivalent that liberate amine by first dissociatingthermally. The amount of aminosilane is between 0.01% and 10% by weightrelative to the functional polymer, preferably between 0.03% and 3%, andmore preferably between 0.1% and 1%.

In some embodiments, the adhesion-promoting reagents can be added to acoating mixture comprising a first organosilane and a liquid crystalsilane, as disclosed herein, and contacted with a substrate (e.g., aglass substrate) under conditions that facilitate the formation ofSi—O—Si linkages, as described herein. The coating mixture can becontacted with a suitable substrate, as described herein. Accordingly,the silane group in the adhesion-promoting reagent can link a firstorganosilane molecule to another first organosilane molecule (which mayoptionally be a component of a polymeric structure), a quaternaryammonium organosilane (e.g., the liquid crystal silane disclosed in U.S.Pat. No. 6,504,582) molecule (which may optionally be a component of apolymeric structure); or the substrate; or the silane group in theadhesion-promoting reagent can link a liquid crystal silane molecule toanother liquid crystal silane molecule (which may optionally be acomponent of a polymeric structure) or to the substrate.

In some embodiments, the adhesion-promoting reagents can be added to acoating mixture comprising a polymer having a plurality of pendantgroups that include a first pendant group that includes a firstquaternary ammonium component, a second pendant group that includes anonpolar component, and subsequently a third pendant group that includesan organosilane or organic silane ester component. Optionally, thecoating mixture further can comprise a first organosilane, as describedherein. The coating mixture can be contacted with a suitable substrateand heated as described herein to facilitate the formation of Si—O—Sibonds.

In an alternative embodiment, one or more adhesion-promoting reagent canbe dissolved in an organic solvent and coated onto a suitable substrate(e.g., glass) as described herein to form a first coating. After removalof the solvent by evaporation, the substrate comprises a layer (i.e., a“primer layer” or “adhesion-promoting” layer) of the adhesion-promotingreagent coated thereon. Subsequently, a composition (e.g., a solution)comprising any antimicrobial polymer of the present disclosure inorganic solvent can be coated onto the primer layer. After removal ofthe solvent by evaporation, the substrate now comprises two layers, the“primer layer” and the antimicrobial polymer layer. The substrate, nowcomprising two coated layers, can be heated (e.g., to about 120 degreesC. for about 3 minutes to about 15 minutes) to facilitate the formationof Si—O—Si bonds and, thereby, covalently couple the polymer to thesubstrate.

Catalysts:

In any embodiment the method of making an antimicrobial coatingaccording the present disclosure, one or more catalyst can be used inthe process. Suitable catalysts include any compound that promotes theformation of Si—O—Si bonds. Nonlimiting examples of suitable catalystsinclude an acid (e.g., an organic acid), a base (e.g., an organic base),tin octoate and 1,8-Diazabicycloundecene (DBU). In any embodiment, thecatalyst can be added with the antimicrobial component and theadhesion-promoting reagent, if present, to the first compositiondescribed herein.

In use, the catalyst can be dissolved in the first composition, secondcomposition, first mixture and/or second mixture described herein.Typically, the final concentration of the catalyst in any coatingcomposition is relatively low (e.g., about 0.04 weight percent). Aperson of ordinary skill in the art will recognize that theconcentration of the catalyst should be sufficiently high enough tocatalyze the cross-linking reaction, while avoiding substantialinterference with the optical properties (e.g., color) of the coatingand/or interference with the shelf-life of the coating mixture.

Substrates and Articles:

Antimicrobial polymers of the present disclosure can be applied as acoating to a variety of substrates. Useful substrates include, forexample, non-siliceous ceramic materials, siliceous materials such asglasses and siliceous ceramic materials, metals, metal oxides, naturaland man-made stones, woven and non-woven fabrics, wood, and polymericmaterials that are either thermoplastic polymers or thermoset polymers.Exemplary polymeric substrates include, but are not limited to, rayonpolyester, polyethylene terephthalate (PET), poly(meth)acrylates,polycarbonates, polystyrenes, polystyrene copolymers such as styreneacrylonitrile copolymers, polyesters, polyethersulfone, acrylics andacrylic copolymers, polyacrylamides, and polyurethanes, and combinationsthereof. Suitable natural polymer substrates include, for example,polylactic acid (PLA), polyglycolic acid (PGA), wood pulp, cotton,cellulose, rayon, and combinations thereof.

The substrates can be used to fabricate a variety of useful articles(e.g., as a part, a portion, or the entirety of the article). Thearticles comprise a variety of surfaces that may be deliberately orincidentally contacted with microbiologically-contaminated items duringroutine use. The articles include, for example, electronic displays(e.g., computer touch screens). Suitable articles may be found infood-processing environments (e.g., food-processing rooms, equipment,countertops) and health care environments (e.g., patient care rooms,countertops, bedrails, patient care equipment such as instruments andstethoscopes, and in-dwelling medical devices such as urinary cathetersand endotracheal tubes).

Methods of Preparing Antimicrobial Coated Articles:

The present disclosure provides methods for coating the antimicrobialpolymer of the present disclosure onto a substrate. The composition(e.g., a reaction mixture in a solution) comprising the antimicrobialpolymer in solvent (e.g., an aqueous solvent, an organic solvent) can becontacted with a substrate. The solvent can be evaporated to leave theantimicrobial polymer in the form of a coating on the substrate. In someembodiments, the substrate can be heated before and/or during thecontacting step to accelerate the evaporation of the solvent.Preferably, the substrate is heated to a temperature that does notdegrade the function of the polymer or a component of the substrate ontowhich the polymer is coated. A suitable temperature for contacting thepolymer solution on a glass substrate is from room temperature to about120° C. A person of ordinary skill in the art will recognize that highertemperatures will facilitate faster removal of organic solvent from thepolymer solution.

In some embodiments, the antimicrobial polymer can be diluted to a finalconcentration of 1 wt. % to about 20 wt % in the organic solvent beforeusing the diluted solution to coat the antimicrobial polymer onto asubstrate. In some embodiments, the antimicrobial polymer is diluted toa final concentration of 1 wt % to about 5 wt % in the organic solventbefore using the diluted solution to coat the antimicrobial polymer ontoa substrate. Suitable organic solvents to dilute the polymer have aflashpoint below 150° C. and include ethers, ketones esters andalcohols, for example, isopropyl alcohol.

Turning back to the drawings, FIG. 4 shows one embodiment of a method ofpreparing a coated article according to the present disclosure. Themethod includes the step 454 of forming a first composition comprisingan antimicrobial polymer in a solvent. The polymer can be formed bymixing a plurality of monomers in a suitable solvent (e.g., an organicsolvent such as isopropyl alcohol, for example) as disclosed herein.Preferably, a relatively small portion (e.g., 3%) of the solventcomprises acidified water. Acidified water in the reaction mixture canfacilitate bonding between silane groups. Optionally, after forming theantimicrobial polymer, the polymer composition can be diluted (notshown) in a solvent, as described above, before contacting it with asubstrate.

The method may include optional step 456 of mixing the first compositionwith a second quaternary ammonium compound and/or a second organosilanecompound to form a first mixture. Suitable second quaternary ammoniumcompounds are described in U.S. Pat. No. 6,504,583; and includeantimicrobial silanated quaternary amine compounds such asN,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-1-octadecanaminium chloride(CAS Number 27668-52-6), for example. Suitable second organosilanecompounds comprise hydrolyzable groups and can facilitate the formationof crosslinks between silanated compounds and/or crosslinks betweensilanated compounds and a siliceous substrate. Examples of suitablesecond organosilane compounds include alkyl halide organosilanecompounds and trimethoxysilyl compounds (e.g.,3-chloropropyltrimethoxysilane).

The method further comprises the step 458 of contacting the firstcomposition with the first substrate under conditions suitable to permitbonding between the antimicrobial polymer and the first substrate.Initially, the first composition, which may optionally include anantimicrobial monomer, is applied to a first substrate. The firstsubstrate may be any of the suitable substrates disclosed herein. Insome embodiments, the first substrate may be a coating (e.g., asiliceous coating) on a second substrate (e.g., a polymer or glasssubstrate). In some embodiments, the first substrate may be glass, apolymer film, or a diamond-like glass material. Suitable diamond-likeglass materials are described in U.S. Pat. Nos. 6,696,157; 6,015,597;and 6,795,636; and U.S. Patent Application Publication No. US2008/196664. The first composition may be applied by a variety ofprocesses known in the art such as, for example, wiping, brushing, dipcoating, curtain coating, gravure coating, kiss coating, spin coating,and spraying.

Contacting the first composition with the substrate further comprisescontacting the first composition under conditions that facilitate theformation of Si—O—Si bonds. A person having ordinary skill in the artwill appreciate that during and after the period which solvent of thefirst composition evaporates, components of the first composition willbegin reacting with each other and/or with the siliceous substrate toform Si—O—Si bonds. This reaction will proceed relatively slowly atambient temperature (circa 23° C.). Heating the substrate can facilitatethe formation of cross-linking covalent bonds between the silane groupsin the antimicrobial coating composition and the silane groups on thesurface of the first substrate. Thus, in certain preferred embodiments,the formation of the Si—O—Si bonds can be accelerated by the optionalstep 460 of exposing the coated substrate to an elevated temperature.Without being bound by theory, other forces (e.g., hydrophobicinteraction, electrostatic forces, hydrogen bonding, and/or adhesion)also may facilitate coupling of components of the antimicrobial coatingcomposition to the first substrate.

In general, exposing the first substrate to higher temperatures whilecontacting it with the polymer composition will require shorter timesfor the solvent to evaporate and for the polymer to bond to the firstsubstrate. However, the contacting step should be performed attemperatures below which the siloxane bonds dissociate. For example, insome embodiments, the contacting step can be conducted at about ambienttemperature (20-25° C.) for about 10 minutes to about 24 hours. In someembodiments, the contacting step can be conducted at about 130° C. forabout 30 seconds to about 3 minutes. The conditions for the contactingstep can have a significant impact on the properties of the polymercoating on the substrate. For example, a polymer contacted (“cured”) atroom temperature for 24 hours can be measurably more hydrophobic than apolymer cured at about 130° C. for about 3 minutes. In some embodiments,the hydrophobicity of the coating correlates with the durability of thepolymer coating on the substrate.

In some embodiments (not shown), the method optionally includespre-treatments of the substrates by priming, plasma etching, corona forinterfacial adhesion of the coating to substrates.

In some embodiments (not shown), the method optionally includes posttreatments of the coating by heating or irradiations including UV, IRplasma, E-beam for further improvement of interfacial adhesion of thecoating to substrates. These treatments can promote inter-polymercrosslinking, as well as increase the number of covalent linkagesbetween the polymer and the substrate, thereby improving the durabilityof the coating on the surface of the substrate. If the first substrateis exposed to an elevated temperature (step 460), the method may includecooling the substrate. Typically, the substrate is cooled to roomtemperature.

In some embodiments, the method optionally includes the step 462 ofcoupling the first substrate to a second substrate. The first substratemay be coupled to the second substrate before or after the step 458 ofcontacting the first composition or first mixture with the firstsubstrate. The second substrate may be any suitable substrate describedherein. For example, the second substrate may be a glass layer orparticle and the first substrate may be a glass or diamond-like coatingand the polymer may be applied to the first substrate after the firstsubstrate is coated onto the second substrate. In an alternativeembodiment, the first substrate may be a polymer film with adhesive onone major surface of the film. In the alternative embodiment, thepolymer composition may be applied to the major surface of the filmopposite the adhesive and the polymer-coated adhesive film maysubsequently be coupled via the adhesive to a second substrate such as aglass or polymer layer, for example.

In some embodiments, the method further comprises a step of applying asiliceous layer to the first substrate. The first substrate may be anysuitable substrate described herein to which a siliceous layer may beapplied. The siliceous layer may be applied by methods that are known toa person of ordinary skill in the art. A nonlimiting example of applyinga siliceous layer to a substrate is described in Example 1 of U.S. Pat.No. 7,294,405; wherein an antiglare hard coat siliceous layer is appliedto a glass substrate. In these embodiments, the method further includesforming a first composition comprising the antimicrobial polymer in asolvent, as described above, for example. Optionally, the theseembodiments may include the step of mixing the first composition with asecond quaternary ammonium compound to form a first mixture, asdescribed above, for example. The method further includes contacting thefirst composition or first mixture to the siliceous layer. The firstcomposition or first mixture can be applied by any suitable coatingmethod, such as the coating methods described herein, for example.Contacting the first composition with the siliceous layer furthercomprises contacting the first composition with the siliceous layerunder conditions suitable to facilitate the formation of Si—O—Si bonds,as described herein. Optionally, contacting the first composition withthe first substrate may further comprise treating the polymer-coatedsubstrate with actinic and/or ionizing radiation (e.g., ultravioletlight, e-beam, plasma, or the like). This treatment can promoteinter-polymer crosslinking, as well as increase the number of covalentlinkages between the polymer and the substrate, thereby improving thedurability of the coating on the surface of the substrate.

It should be noted that, in any embodiment of the methods disclosedherein, pretreatment of siliceous layers or substrates prior to applyingantimicrobial polymer compositions of the present disclosure can improvethe bonding between the polymer and the substrate (e.g., siliceousmaterial). Pretreatment of the siliceous layer or the substrate mayinclude, for example, soaking the layer or the substrate in a volatilesolvent (e.g., water, isopropyl alcohol) and/or wiping the layer or thesubstrate with the volatile solvent. Optionally, the solvent may furthercomprise a solution of a basic compound such as potassium hydroxide, forexample. In some embodiments, the solvent may be saturated with thesolution of the basic compound.

In particular, pretreatments that include heating the siliceous layer orthe substrate from about 100 degrees to about 150 degrees for 20 minutesto 60 minutes can improve the bonding between the polymer and thesubstrate. Other suitable heat treatments include exposing the siliceoussubstrate to a temperature from about 475 to about 550 degrees C. for aduration of at least about 3 minutes or longer; preferably, for about 3minutes to about 10 minutes; more preferably, for about 6 minutes toabout 10 minutes. In some embodiments, pretreatment by heating thesubstrate shortly before the antimicrobial coating is applied results inimproved bonding (e.g., as measured by the durability of the coating)between the coating and the substrate. The improved bonding can resultin significantly greater durability of the polymer layer on thesubstrate. This can be demonstrated, for example, using the Eraser Testdescribed herein. Without being bound by theory, it is believed thatpretreatment of the substrate by heating removes excess moisture andother impurities (e.g., organic residues) present on the surface of thesubstrate (e.g., siliceous material) and provides greater ability of thesurface silane groups to react with the silanated polymers and/orcompounds in the coating compositions disclosed herein.

Embodiments

Embodiment A is an article, comprising:

an organic polymer having a plurality of pendant groups comprising

-   -   a first pendant group comprising a first quaternary ammonium        component;    -   a second pendant group comprising a nonpolar component;    -   a third pendant group comprising a first organosilane component;        and

a touch-sensitive substrate comprising a surface;

wherein the organic polymer is coupled to the surface.

Embodiment B is the article of embodiment A, further comprising asiliceous substrate that includes a first side and a second side,wherein the organic polymer is coupled to the first side of thesiliceous substrate, and wherein the touch-sensitive substrate iscoupled to the second side of the siliceous substrate.

Embodiment C is the article of embodiment A or embodiment B, wherein thearticle does not comprise a conductive layer.

Embodiment D is the article of any one of the preceding embodiments,wherein the organic polymer further comprises a second quaternaryammonium component.

Embodiment E is the article of any one of the preceding embodiments,wherein the organic polymer further comprises a second organosilanecomponent.

Embodiment F is the article of embodiment E, wherein the secondorganosilane component comprises an alkyl halide.

Embodiment G is the article of any one of the preceding embodimentswherein, in the organic polymer, the ratio of the number of N atomsassociated with the first quaternary ammonium component and secondquaternary ammonium component, if present, and the number of Si atomsassociated with the first organosilane component and second organosilanecomponent, if present, is about 0.1:1 to about 10:1.

Embodiment H is the article of any one of the preceding embodiments,wherein at least one of the pendant components comprises afluorochemical.

Embodiment I is the article of embodiment H, wherein the second pendantgroup comprises a fluorochemical.

Embodiment J is the article of any one of the preceding embodiments,wherein the contact angle of deionized water deposited on the curedpolymer is about 80° to about 120°, using the ASTM D 7334.7606-1 testmethod.

Embodiment K is the article of embodiment J, wherein the contact angleof deionized water deposited on the cured polymer is about 85° to about110°, as measured by ASTM test method number D 7334.7606-1.

Embodiment L is the article of any one of the preceding embodiments,wherein the scratch resistance of the cured polymer is about #5 to about#8 Moh's hardness, as measured by ASTM test method number D 7027.26676.

Embodiment M is the article of any one of the preceding embodiments,wherein the surface to which the organic polymer is coupled is a glassor a polymeric surface.

Embodiment N is the article of any one of the preceding embodiments,wherein the siliceous substrate is covalently coupled to thetouch-sensitive substrate.

Embodiment O is the article of any one of embodiments A through P,wherein the substrate further comprises an antiglare component.

Embodiment P is a method of making a coated article, the methodcomprising:

forming a first composition of an organic polymer in organic solvent,the polymer having a plurality of pendant groups comprising,

-   -   a first pendant group comprising a first quaternary ammonium        component,    -   a second pendant group comprising a nonpolar component, and    -   a third pendant group comprising a first organosilane component;

mixing a second quaternary ammonium component with the first compositionto form a first mixture; and

contacting the first mixture with a substrate under conditions suitableto form covalent linkages between the organic polymer, the substrate,and the second quaternary ammonium component.

Embodiment Q is the method of embodiment P, wherein forming a firstmixture further comprises forming a first mixture that includes acatalyst compound.

Embodiment R is the method of embodiment P or embodiment Q, whereinforming a first mixture further comprises forming a first mixturecomprising a second organosilane component.

Embodiment S is the method of any one of embodiments P through R,further comprising coupling the substrate to a touch-sensitivesubstrate.

Embodiment T is the method of embodiment S, wherein coupling thesiliceous substrate to the touch-sensitive substrate comprisescovalently coupling the siliceous substrate to the touch-sensitivesubstrate.

Embodiment U is a method of making a coated article, the methodcomprising:

forming a first composition of an organic polymer in organic solvent,the polymer having a plurality of pendant groups comprising,

-   -   a first pendant group comprising a first quaternary ammonium        component,    -   a second pendant group comprising a nonpolar component, and    -   a third pendant group comprising a first organosilane component;

mixing an adhesion-promoting reagent with the first composition to forma second mixture; and

contacting the second mixture with a substrate under conditions suitableto form covalent linkages between the organic polymer and the substrate.

Embodiment V is the method of embodiment U, wherein forming a secondmixture further comprises forming a first composition that includes acatalyst compound.

Embodiment W is the method of embodiment U or embodiment V, whereinforming a second mixture further comprises forming a second mixturecomprising a second quaternary ammonium component.

Embodiment X is the method of any one of embodiments U through W,wherein forming a second mixture further comprises forming a secondmixture comprising a second organosilane component.

Embodiment Y is the method of any one of embodiments U through X,wherein the adhesion-promoting reagent is selected from the groupconsisting of 3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.

Embodiment Z is The method of any one of embodiments P through Y,further comprising:

contacting a second composition comprising an adhesion-promoting reagentin organic solvent with the siliceous substrate under conditionssuitable to form covalent linkages between the adhesion-promotingreagent and the siliceous substrate;

wherein contacting the second composition with the siliceous substrateoccurs prior to contacting the first or second mixture with thesiliceous substrate.

Embodiment AA is the method of embodiment Z, wherein contacting thesecond composition with the siliceous substrate further comprisescontacting the second composition with the siliceous substrate at atemperature higher than 25° C.

Embodiment BB is a method of making a coated article, the methodcomprising:

forming a first composition of an organic polymer in organic solvent,the polymer having a plurality of pendant groups comprising,

-   -   a first pendant group comprising a first quaternary ammonium        component,    -   a second pendant group comprising a nonpolar component, and    -   a third pendant group comprising a first organosilane component;

mixing a second quaternary ammonium component with the first compositionto form a first mixture; and

contacting the first mixture with a touch-sensitive substrate underconditions suitable to form covalent linkages between organic polymerand the touch-sensitive substrate.

Embodiment CC is the method of embodiment BB, wherein forming a firstmixture further comprises forming a first mixture that includes acatalyst compound.

Embodiment DD is the method of embodiment BB or embodiment CC, whereinmixing a second quaternary ammonium component with the first compositionfurther comprises mixing a second organosilane component with the firstcomposition.

Embodiment EE is the method of any one of embodiments BB through DD,further comprising, after the contacting step, rinsing the coatedarticle.

Embodiment FF is a method of making a coated article, the methodcomprising:

forming a first composition of an organic polymer in organic solvent,the polymer having a plurality of pendant groups comprising,

-   -   a first pendant group comprising a first quaternary ammonium        component,    -   a second pendant group comprising a nonpolar component, and    -   a third pendant group comprising a first organosilane component;

mixing an adhesion-promoting reagent with the first composition to forma second mixture; and

contacting the second mixture with a touch-sensitive substrate underconditions suitable to form covalent linkages between organic polymer,the touch-sensitive substrate, and the second quaternary ammoniumcomponent.

Embodiment GG is the method of embodiment FF, wherein forming a secondmixture further comprises mixing a second quaternary ammonium componentwith the adhesion-promoting reagent and the first composition.

Embodiment HH is the method of embodiment FF or embodiment GG, whereinthe adhesion-promoting reagent is selected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.

Embodiment II is the method of any one of embodiments BB through HH,further comprising:

providing a second composition comprising a adhesion-promoting reagentin organic solvent;

contacting the second composition with the touch-sensitive substrate;

wherein contacting a second composition with the touch-sensitivesubstrate occurs prior to contacting the first or second mixture withthe siliceous substrate.

Embodiment JJ is an antimicrobial composition, comprising:

an organic polymer having a plurality of pendant groups comprising

-   -   a first pendant group comprising a first quaternary ammonium        component;    -   optionally, a second pendant group comprising a perfluorinated        nonpolar component; and    -   a third pendant group comprising a first organosilane component;

with the proviso that the polymer does not comprise a pendant group thatincludes a carboxylate or alkoxylate chemical group.

Embodiment KK is the antimicrobial composition of embodiment JJ, furthercomprising a fourth pendant component, wherein the fourth pendantcomponent comprises a polar chemical group.

Embodiment LL is a composition, comprising:

a solvent;

a polymer having a plurality of pendant groups comprising,

a first pendant group comprising a first quaternary ammonium component,

-   -   a second pendant group comprising a nonpolar component, and    -   a third pendant group comprising a first organosilane component;        and

an adhesion-promoting reagent.

Embodiment MM is the composition of embodiment LL, wherein theadhesion-promoting reagent is selected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl) phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.

Embodiment NN is an article, comprising:

a touch-sensitive substrate comprising a surface;

a first layer coated on the surface, the first layer comprising anadhesion-promoting reagent; and

a second layer coated on the first layer, the second layer comprising anorganic polymer having a plurality of pendant groups comprising

-   -   a first pendant group comprising a first quaternary ammonium        component;    -   a second pendant group comprising a nonpolar component;    -   a third pendant group comprising a first organosilane component.

Embodiment OO is the article of embodiment NN, wherein theadhesion-promoting reagent is selected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.

The invention will be further illustrated by reference to the followingnon-limiting Examples. All parts and percentages are expressed as partsby weight unless otherwise indicated.

EXAMPLES

The present invention is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present inventionwill be apparent to those skilled in the art. Unless otherwise noted,all parts, percentages, and ratios reported in the following examplesare on a weight basis, and all reagents used in the examples wereobtained, or are available, from the chemical suppliers described below,or may be synthesized by conventional techniques.

A list of reagents used in the following examples in shown in Table 1.

TABLE 1 Abbreviation Chemical Name Source 2EHA 2-Ethylhexyl acrylateDow; Midland, MI A-174 Methacryloylpropyl trimethoxy silane Aldrich;Milwaukee, WI AA Acrylic acid BASF; Florham, NJ A1120 N(beta-aminoethyl)gamma- ShinEtsu; Akron, OH aminopropyltrimethoxysilane AEM57003-(trimethoxysilyl)- Aegis Environmental, propyldimethyloctadecylammonium Midland, MI chloride BHT 2,6-Di-tert-4-methyl phenol Aldrich;Milwaukee, WI C₁₆H₃₃Br 1-bromohexyl decane Chemtura Corporation, BayMinette, AL C4FA Perfluorobutyl sulfonamide n-methyl ethyl Made asdescribed in acrylate U.S. Pat. No. 6,852,781 DMAc Dimethyl acrylamideJarchem Industries, Inc. Newark, NJ DMAEA Dimethylaminoethyl acrylateCIBA; Marietta, GA DMAEA- Dimethylaminoethyl acrylate C16 bromide SeeExample 2 C16Br DMAEA-MCl Dimethylaminoethyl acrylate methyl CIBA;Marietta, GA chloride DMAEMA Dimethylaminoethyl methacrylate CIBA;Marietta, GA DMAEMA- Dimethylaminoethyl methacrylate C16 See Example 1C16Br bromide DMAEMA- Dimethylaminoethyl methacrylate methyl CIBA;Marietta, GA MCl chloride EOA Methoxy polyethylene glycol acrylate ShinNakamura Chemicals; Wakayama, JP EOMA polyethyleneglycolmonomethacrylate Nippon Nyukazai Co; Tokyo, JP EtOAc Ethyl acetate J.T.Baker; Austin, TX EtOH Ethanol J.T. Baker; Austin, TX HEMA Hydoxyethylmethacrylate Cyro Industries; Parsippany, NJ HFPOA Hexafluoropropyleneoxide oligomer U.S. Patent Application amidol acrylate Publication No.2004/0077775 HFPOMA Hexafluoropropylene oxide oligomer U.S. PatentApplication amidol methacrylate Publication No. 2004/0077775 IBMAIsobutyl methacrylate Lucite International, Inc. Cordova, TN IOAIso-octyl acrylate Sartomer USA, LLC; Exton, PA IPA Isopropyl alcoholVWR; Houston, TX MEHQ 4-Methoxyphenol Alfa Aesar, Ward Hill, MA NHMAcN-(hydroxymethyl)-acrylamide Aldrich; Milwaukee, WI NVPN-Vinylpyrrolidinone ISP Chemicals, Inc.; Calvary City, KY SnOATin-octoate Alfa Aesar, Ward Hill, MA Vazo-672,2-Azobis(2-methylbutyronitrile) Dupont; Wilmington, DE

Example 1 Synthesis of DMAEMA-C₁₆Br Monomer

In a clean reactor; fitted with an overhead condenser, mechanicalstirrer, and a temperature probe; were charged 918 parts by weight ofacetone, 807 parts of C₁₆H₃₃Br) 415.5 parts of DMAEMA, 2.0 parts of BHTand 2.0 parts of MEHQ. The batch was stirred at 150 rpm and a mixed gas(90/10 O₂/N₂) was purged through the solution throughout the reactionscheme. The mixture was heated to 74° C. for 18 hours. A sample wastaken out for analysis by gas chromatography (GC) and which revealed theconversion of >98% of the reactants to the desired product. At thispoint 918 parts of EtOAc was added slowly with stirring at very highspeed. A white solid started to precipitate out. The heating was stoppedand the mixture was cooled to room temperature. The reaction precipitatewas recovered by filtration and the white solid material was washed with200 parts of cold EtOAc. The solid material was dried in a vacuum ovenat 40° C. for 8 hours. The dried product was analyzed by nuclearmagnetic resonance (NMR) spectroscopy, which revealed the presenceof >99.9% pure DMAEMA-C₁₆Br monomer.

Example 2 Synthesis of DMAEA-C₁₆Br Monomer

In a clean reactor; fitted with an overhead condenser, mechanicalstirrer, and a temperature probe; were charged 546 parts of acetone, 488parts of C₁₆H₃₃Br, 225 parts of DMAEA, 1.0 parts of BHT and 1.0 parts ofMEHQ. The batch was stirred at 150 rpm and a mixed gas (90/10 O₂/N₂) waspurged through the solution throughout the reaction scheme. The mixturewas heated to 74° C. for 18 hours. A sample was taken out for analysisby GC and it revealed the conversion of >98% of the reactants to thedesired product. At this point the reaction mixture heating was stoppedand 1,000 parts of EtOAc was added slowly with stirring at very highspeed. A white solid started to precipitate out. The mixture was allowedto cool to room temperature. The precipitate accumulated in the solutionupon standing for couple of hours at room temperature. The reactionmixture was filtered and the white solid filtrate was washed with 1,000parts of cold EtOAc. The white solid filtrate was dried in a vacuum ovenat 40° C. for 8 hours. The solid material was analyzed by NMRspectroscopy, which revealed the presence of >99.9% pure DMAEA-C₁₆Brmonomer.

Examples 3-39 Synthesis of Antimicrobial Polymers

In a clean reaction bottle, the monomers (e.g., in Example 6, 50 partsof DMAEMA-C₁₆Br monomer, 10 parts of A-174 monomer, and 40 parts of IOAmonomer) were combined with 0.5 parts of Vazo-67 and 300 parts of IPA.The mixture was purged with dry nitrogen for 3 minutes. The reactionbottle was sealed and placed in a 65° C. preheated water bath withmixing. The reaction mixture was heated for 17 hours at 65° C. withmixing. The viscous reaction mixture was analyzed for % solids. To drivethe reaction of the residual monomer to >99.5% completion, an additional0.1 parts of Vazo-67 was added to the mixture, the solution was purgedand sealed. The bottle was placed in the 65° C. water bath with mixingand heated for 8 hours. A conversion of (>99.5%) of the monomers wasachieved, as evident by % solids calculation.

The polymers shown in Table 2 each were made according to this process.Table 2 lists the polymers that were synthesized in each Example.Comparative examples, which do not comprise an organosilane pendantgroup, are so designated in Table 2.

TABLE 2 Antimicrobial polymers. The polymer designation (e.g.,“p(DMAEMA- C16Br/A-174/IBMA)” in Example 4) refers to the combination ofmonomers used in the reaction mixture. Comparative examples, which donot comprise an organosilane pendant group, are designated with thenotation “comparative”. Example # Polymer Designation Monomer Ratio  3comparative p(DMAEMA-C₁₆Br/AA/IOA) 50/20/30  4p(DMAEMA-C16Br/A-174/IBMA) 50/10/40  5 p(DMAEA-MCl/A-174/IBMA) 50/10/40 6 p(DMAEMA-C16Br/A-174/IOA) 50/10/40  7 comparativep(DMAEMA-C₁₆Br/AA/IOA) 50/20/30  8 p(DMAEMA-C16Br/A-174/NHMAc/IOA50/10/10/30  9 comparative p(DMAEMA-C16Br/HEMA/NHMAc/IOA 50/10/10/30 10p(DMAEMA-C16Br/A-174/DMAc/IOA 50/10/10/30 11 comparativep(DMAEMA-C16Br/HEMA/DMAc/IOA 50/10/10/30 12 comparativep(DMAEMA-C16Br/AA/IBMA 50/20/30 13 comparative p(DMAEMA-C16Br/AA/2EHA50/20/30 14 comparative p(DMAEMA-C16Br/HFPOMA/AA) 50/20/30 15comparative p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 50/20/10/20 16 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA) 50/20/10/20 17 comparativep(DMAEMA-C16Br/HFPOMA/DMAc/AA) 50/20/10/20 18 comparativep(DMAEMA-C16Br/HFPOA/AA) 50/20/30 19 comparativep(DMAEMA-C16Br/HFPOA/HEMA/AA) 50/20/10/20 20 comparativep(DMAEMA-C16Br/HFPOA/DMAc/AA) 50/20/10/20 21 comparativep(DMAEMA-C16Br/HFPOA/EOA/AA) 50/20/10/20 22 comparativep(DMAEMA-C16Br/HFPOA/IOA/AA) 50/20/20/10 23 p(DMAEA-C16Br/A-174/AA/IBMA)50/5/5/40 24 p(DMAEA-C16-Br/A-174/AA/IOA) 50/5/5/40 25p(DMAEMA-C16Br/EOMA/A-174/HFPOMA) 50/20/10/20 26p(DMAEMA-C16Br/HEMA/A-174/HFPOMA) 50/20/10/20 27p(DMAEMA-C16Br/A-174/NHMAc/IOA) 50/10/10/30 28p(DMAEMA-C16Br/A-174/NVP/IOA) 50/5/15/30 29p(DMAEMA-C16Br/A-174/NHMAc/IOA/EOA) 50/5/10/10/25 30p(DMAEA-C16Br/A-174/NHMAc/IOA) 50/10/10/30 31 p(DMAEA-MCl/A-174/EOA/IOA)50/5/20/25 32 p(DMAEMA-C16Br/A-174/IOA) 50/10/40 33 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA) 50/20/10/20 34p(DMAEMA-C16Br/A-174/IOA/AA) 50/10/30/10 35 p(DMAEMA-C16Br/C4FA/A-174/AA50/20/10/20 36 p(DMAEA-C16Br/A-174/IOA) 50/10/40 37p(DMAEA-C16Br/A-174/IOA/AA 50/10/30/10 38p(DMAEA-C16Br/DMAEA-MC1/A-174/IOA 25/25/10/40 39p(DMAEA-C16Br/A-174/NVP/IOA 50/5/15/30

Examples 40-62 Method of Coating Antimicrobial Polymers onto ConductiveSurface Capacitive Touch (SCT) Sensor Glass Substrates

Conductively-coated glass (part number 29617) was obtained fromPilkington North America, Inc. (Toledo, Ohio). A glare-resistanthardcoat was applied to the glass according to the method described inExample 1 of U.S. Pat. No. 7,294,405. The coated glass was cut intocoupons, approximately 4″ by 4″ (10.2 cm by 10.2 cm), for coating andtesting purposes.

Polymer solutions from the Examples shown in Table 3 were diluted inisopropyl alcohol to 5 wt % polymer. Approximately 5 milliliters of thediluted polymer solution were applied to a wipe (Sealed Edge Wiper6259HC; Coventry, Kennesaw, Ga.), which was used immediately to manuallydistribute the polymer solution evenly over the surface of the glasscoupon. The solvent was removed by heating the sample at 120° C. in aconvection oven for 3-4 minutes. After completely removing the solvent,the glass coupons were washed with soap (Optisolve OP7153-LF detergent;available from Kyzen North America (Manchester, N.H.) and deionizedwater in a 36″ Billco Versa Clean Washer (Billco Manufacturing, Inc.,Zelienople, Pa.) with attached fluid head and roller wash pan and dried.The dried samples were tested as described below.

TABLE 3 Polymer-coated SCT glass substrates. Comparative examples, whichdo not comprise an organosilane pendant group, are designated with thenotation “comparative”. Polymer Example Example No. Polymer DesignationNo. 40 p(DMAEMA-C16Br/A-174/IBMA) 4 41 p(DMAEA-MCl/A-174/IBMA) 5 42p(DMAEMA-C16Br/A-174/IOA) 6 43 comparative p(DMAEMA-C16Br/AA/IOA) 7 44p(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 45 comparativep(DMAEMA-C16Br/HEMA/NHMAc/IOA) 9 46 p(DMAEMA-C16Br/A-174/DMAc/IOA) 10 47comparative p(DMAEMA-C16Br/HEMA/DMAc/IOA) 11 48 comparativep(DMAEMA-C16Br/AA/IBMA) 12 49 comparative p(DMAEMA-C16Br/AA/2EHA) 13 50comparative p(DMAEMA-C16Br/HFPOMA/AA) 14 51 comparativep(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 52 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 53 comparativep(DMAEMA-C16Br/HFPOMA/DMAc/AA) 17 54 comparativep(DMAEMA-C16Br/HFPOA/AA) 18 55 comparative p(DMAEMA-C16Br/HFPOA/HEMA/AA)19 56 comparative p(DMAEMA-C16Br/HFPOA/DMAc/AA) 20 57 comparativep(DMAEMA-C16Br/HFPOA/EOA/AA) 21 58 comparativep(DMAEMA-C16Br/HFPOA/IOA/AA) 22 59 p(DMAEA-C16BrA-174/AA/IBMA) 23 60p(DMAEA-C16-Br/A-174/AA/IOA) 24 61 p(DMAEMA-C16Br/EOMA/A-174/ 25 HFPOMA)62 p(DMAEMA-C16Br/HEMA/A-174/ 26 HFPOMA)

Examples 63-86 Method of Coating Hybrid Antimicrobial Polymers ontoConductive Touch (SCT) Glass Substrates

AEM5700 antimicrobial solution was obtained from Aegis Environmental(Midland, Mich.). The AEM5700 was diluted to 1 wt % into IPA to make theworking solution. Conductively-coated glass coupons were prepared asdescribed in Examples 40-62. Polymer solutions from the Examples shownin Table 2 were diluted in IPA to 5 wt %. The diluted polymer solutionswere mixed 1:1 with the working solution of AEM5700. The resultingmixtures (listed in Table 4) were applied to the glass coupons and thehybrid antimicrobial polymer-coated coupons were treated, cleaned, anddried as described in Examples 40-62.

A control (Example 86) consisted of applying 5 milliliters of theAEM5700 working solution directly to a glass coupon and treating,cleaning, and drying the coupon as described for Examples 59-62.

TABLE 4 Hybrid antimicrobial polymer-coated SCT glass substrates.Comparative examples, which do not comprise an organosilane pendantgroup, are designated with the notation “comparative”. Example No.Hybrid Polymer Designation Polymer Example No. 63p(DMAEMA-C16Br/A-174/IBMA/AEM) 4 64 p(DMAEA-MCl/A-174/IBMA/AEM) 5 65p(DMAEMA-C16Br/A-174/IOA/AEM) 6 66 comparativep(DMAEMA-C16Br/AA/IOA/AEM) 7 67 p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8 68comparative p(DMAEMA-C16Br/HEMA/NHMAc/IOA/AEM) 9 69p(DMAEMA-C16Br/A-174/DMAc/IOA/AEM) 10 70 comparativep(DMAEMA-C16Br/HEMA/DMAc/IOA/AEM) 11 71 comparativep(DMAEMA-C16Br/AA/IBMA/AEM) 12 72 comparativep(DMAEMA-C16Br/AA/2EHA/AEM) 13 73 comparativep(DMAEMA-C16Br/HFPOMA/AA/AEM) 14 74 comparativep(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 75 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 76 comparativep(DMAEMA-C16Br/HFPOMA/DMAc/AA/AEM) 17 77 comparativep(DMAEMA-C16Br/HFPOA/AA/AEM) 18 78 comparativep(DMAEMA-C16Br/HFPOA/HEMA/AA/AEM) 19 79 comparativep(DMAEMA-C16Br/HFPOA/DMAc/AA/AEM) 20 80 comparativep(DMAEMA-C16Br/HFPOA/EOA/AA/AEM) 21 81 comparativep(DMAEMA-C16Br/HFPOA/IOA/AA/AEM) 22 82 p(DMAEA-C16BrA-174/AA/IBMA/AEM)23 83 p(DMAEA-C16-Br/A-174/AA/IOA/AEM) 24 84 p(DMAEMA-C16Br/EOMA/A- 25174/HFPOMA/AEM) 85 P(DMAEMA-C16Br/HEMA/A- 26 174/HFPOMA/AEM) 86 NoPolymer - AEM5700 Control —

Examples 87-109 Method of Coating Antimicrobial Polymers onto DispersiveSignal Technology (DST) Glass Substrates

Chemstrengthened glass (2.2 mm flowed glass; part no. 37373.2) wasobtained from EuropTec USA, Inc. (Clarksburg, W. Va.). The glass was cutinto coupons, approximately 4″ by 4″ (10.2 cm by 10.2 cm), for coatingand testing purposes.

Polymer solutions from the Examples shown in Table 3 were diluted inisopropyl alcohol to 5 wt % polymer. Approximately 5 milliliters of thediluted polymer solution were applied to a wipe (Sealed Edge Wiper6259HC; Coventry, Kennesaw, Ga.), which was used immediately to manuallydistribute the polymer solution evenly over the surface of the glasscoupon. The solvent was removed by heating the sample at 120° C. in aconvection oven for 3-4 minutes. After completely removing the solvent,the glass coupons were washed with soap (Optisolve OP7153-LF detergent;available from Kyzen North America (Manchester, N.H.) and deionizedwater in a 36″ Billco Versa Clean Washer (Billco Manufacturing, Inc.,Zelienople, Pa.) with attached fluid head and roller wash pan and dried.The dried samples were tested as described below.

TABLE 5 Polymer-coated DST glass substrates. Comparative examples, whichdo not comprise an organosilane pendant group, are designated with thenotation “comparative”. Polymer Exam- Example No. Polymer Designationple No. 87 p(DMAEMA-C16Br/A-174/IBMA) 4 88 p(DMAEA-MCl/A-174/IBMA) 5 89p(DMAEMA-C16Br/A-174/IOA) 6 90 comparative p(DMAEMA-C16Br/AA/IOA) 7 91P(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 92 comparativeP(DMAEMA-C16Br/HEMA/NHMAc/IOA) 9 93 p(DMAEMA-C16Br/A-174/DMAc/IOA) 10 94comparative p(DMAEMA-C16Br/HEMA/DMAc/IOA) 11 95 comparativep(DMAEMA-C16Br/AA/IBMA) 12 96 comparative p(DMAEMA-C16Br/AA/2EHA) 13 97comparative p(DMAEMA-C16Br/HFPOMA/AA) 14 98 comparativeP(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 99 comparativeP(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 100 comparative P(DMAEMA-C16Br/HFPOMA/DMAc/AA) 17 101 comparative p(DMAEMA-C16Br/HFPOA/AA) 18 102 comparative p(DMAEMA-C16Br/HFPOA/HEMA/AA) 19 103 comparative p(DMAEMA-C16Br/HFPOA/DMAc/AA) 20 104 comparative p(DMAEMA-C16Br/HFPOA/EOA/AA) 21 105 comparative p(DMAEMA-C16Br/HFPOA/IOA/AA) 22 106  p(DMAEA-C16BrA-174/AA/IBMA) 23 107 p(DMAEA-C16-Br/A-174/AA/IOA) 24 108  p(DMAEMA-C16Br/EOMA/A-174/ 25HFPOMA) 109  p(DMAEMA-C16Br/HEMA/A-174/ 26 HFPOMA)

Examples 110-133 Method of Coating Hybrid Antimicrobial Polymers ontoDispersive Signal Technology (DST) Glass Substrates

AEM5700 antimicrobial solution was obtained from Aegis Environmental(Midland, Mich.). The AEM5700 was diluted to 1 wt % into IPA to make theworking solution. DST glass coupons were prepared as described inExamples 87-109. Polymer solutions from the Examples shown in Table 2were diluted in IPA to 5 wt %. The diluted polymer solutions were mixed1:1 with the working solution of AEM5700. The resulting mixtures (shownin Table 6) were applied to the glass coupons and the hybridantimicrobial polymer-coated coupons were treated, cleaned, and dried asdescribed in Examples 87-109 and were tested as described below.

A control (Example 133) consisted of applying 5 milliliters of theAEM5700 working solution directly to a glass coupon and treating,cleaning, and drying the coupon as described for Examples 87-109.

TABLE 6 Hybrid antimicrobial polymer-coated DST glass substrates.Comparative examples, which do not comprise an organosilane pendantgroup, are designated with the notation “comparative”. Polymer ExampleNo. Hybrid Polymer Designation Example No. 110p(DMAEMA-C16Br/A-174/IBMA/AEM) 4 111 p(DMAEA-MCl/A-174/IBMA/AEM) 5 112p(DMAEMA-C16Br/A-174/IOA/AEM) 6 113 comparativep(DMAEMA-C16Br/AA/IOA/AEM) 7 114 p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8115 comparative p(DMAEMA-C16Br/HEMA/NHMAc/IOA/AEM) 9 116p(DMAEMA-C16Br/A-174/DMAc/IOA/AEM) 10 117 comparativep(DMAEMA-C16Br/HEMA/DMAc/IOA/AEM) 11 118 comparativep(DMAEMA-C16Br/AA/IBMA/AEM) 12 119 comparativep(DMAEMA-C16Br/AA/2EHA/AEM) 13 120 comparativep(DMAEMA-C16Br/HFPOMA/AA/AEM) 14 121 comparativep(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 122 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 123 comparativep(DMAEMA-C16Br/HFPOMA/DMAc/AA/AEM) 17 124 comparativep(DMAEMA-C16Br/HFPOA/AA/AEM) 18 125 comparativep(DMAEMA-C16Br/HFPOA/HEMA/AA/AEM) 19 126 comparativep(DMAEMA-C16Br/HFPOA/DMAc/AA/AEM) 20 127 comparativep(DMAEMA-C16Br/HFPOA/EOA/AA/AEM) 21 128 comparativep(DMAEMA-C16Br/HFPOA/IOA/AA/AEM) 22 129 p(DMAEA-C16BrA-174/AA/IBMA/AEM)23 130 p(DMAEA-C16-Br/A-174/AA/IOA/AEM) 24 131p(DMAEMA-C16Br/EOMA/A-174/HFPOMA/AEM) 25 132 p(DMAEMA-C16Br/HEMA/A- 26174/HFPOMA/AEM) 133 No Polymer - AEM5700 Control —

Examples 134-143 Method of Coating Antimicrobial Polymers onto ProjectedCapacitive Touch (PCT) Sensor Glass Substrates

TPK antiglare top glass (1.1 mm thick; part no. AG-90) was obtained fromTPK Touch Solutions (Xiamen Headquarters, Fujian, China)). The glass wascut into coupons, approximately 4″ by 4″ (10.2 cm by 10.2 cm), forcoating and testing purposes. Just prior to coating with theantimicrobial polymer solutions, the glass coupons were heated to 130°C. in a convection oven for 30 minutes.

Polymer solutions from the Examples shown in Table 3 were diluted inisopropyl alcohol to 5 wt % polymer. Approximately 5 milliliters of thediluted polymer solution were applied to a wipe (Sealed Edge Wiper6259HC; Coventry, Kennesaw, Ga.), which was used immediately to manuallydistribute the polymer solution evenly over the surface of the PCT glasscoupon. In Examples 134-138, the solvent was removed by allowing thesamples to air-dry at 20° C. for 24 hours. In Examples 139-143, thesolvent was removed by heating the sample at 120° C. in a convectionoven for 3 minutes. After completely removing the solvent, the glasscoupons were wiped with a clean, dry wipe that was identical to the wipethat was used to coat the polymers onto the glass. The dried sampleswere tested as described below.

TABLE 7 Polymer-coated PCT glass substrates. Comparative examples, whichdo not comprise an organosilane pendant group, are designated with thenotation “comparative”. Polymer Exam- Example No. Polymer Designationple No. 134 p(DMAEMA-C16Br/A-174/IOA) 6 135 comparativep(DMAEMA-C16Br/AA/IOA) 7 136 p(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 137comparative p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 138 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 139 p(DMAEMA-C16Br/A-174/IOA) 6 140comparative p(DMAEMA-C16Br/AA/IOA) 7 141 p(DMAEMA-C16Br/A-174/NHMAc/IOA)8 142 comparative p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 143 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16

Examples 144-155 Method of Coating Hybrid Antimicrobial Polymers ontoProjected Capacitive Touch (PCT) Sensor Glass Substrates

AEM5700 antimicrobial solution was obtained from Aegis Environmental(Midland, Mich.). The AEM5700 was diluted to 1 wt % into IPA to make theworking solution. PCT glass coupons were prepared as described inExamples 134-143. Polymer solutions from the Examples shown in Table 2were diluted in IPA to 5 wt %. The diluted polymer solutions were mixed1:1 with the working solution of AEM5700. The resulting mixtures (shownin Table 8) were applied to the glass coupons and the hybridantimicrobial polymer-coated coupons were treated, dried, and cleaned asdescribed in Examples 134-143 and were tested as described below.

Controls (Examples 149 and 155) consisted of applying 5 milliliters ofthe AEM5700 working solution directly to a glass coupon and treating,cleaning, and drying the coupon as described for Examples 134-143.

TABLE 8 Hybrid antimicrobial polymer-coated PCT glass substrates.Comparative examples, which do not comprise an organosilane pendantgroup, are designated with the notation “comparative”. Example No.Polymer Designation Polymer Example No. 144P(DMAEMA-C16Br/A-174/IOA/AEM) 6 145 comparativep(DMAEMA-C16Br/AA/IOA/AEM) 7 146 p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8147 comparative p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 148 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 149 No Polymer - AEM5700 Control —150 p(DMAEMA-C16Br/A-174/IOA/AEM) 6 151 comparativep(DMAEMA-C16Br/AA/IOA/AEM) 7 152 p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8153 comparative p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 154 comparativep(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 155 No Polymer - AEM5700 Control —

Example 156 Physical Testing for Antimicrobial Polymer-Coated GlassSubstrates and Hybrid Antimicrobial Polymer-Coated Glass Substrates

ASTM test methods are published by ASTM International (WestConshohocken, Pa.). The coated glass substrates were tested for avariety of physical properties. The hydrophobicity of the polymer-coatedsurface was tested by measuring the contact angle of a drop of deionizedwater using the ASTM D7334.7606 test method. The scratch resistance ofthe polymer-coated surface was tested using the ASTM D7027-05 test(“Scratch test”) with a constant load of 1000 g using Moh's hardnesspens. The result is reported as the hardest pen that did not cause ascratch with the 1000 g load. The transmitted haze and transmittance ofthe polymer-coated glass substrates were measured using the ASTM D 1003on the Haze Gard Plus meter, from BYK-Gardner GmbH, Geretsried, Germany,and transmission is reported as the percent of light transmitted throughthe sample. The clarity was measured using a BYK-Gardner Haze Gard Plusinstrument, calibrated using 0% (Black cover) standard and a claritystandard of 77.8% provided by BYK-Garner (catalog #4732). Reflected Hazeis measured according to test method ASTM E430. Gloss at 20° and 60° wasmeasured on a BYK Gloss meter using ASTM D523 test method.

The eraser rub test, which is a measurement of the durability of thecoating, was performed according to the United States MilitarySpecification for the Coating of Optical Glass Elements (MIL-C-675C)dated 22 Aug. 1980. The value reported is the number of eraser rubsrequired to remove the coating from the glass.

Tables 9-11 show the results of screening a variety of antimicrobialpolymer and hybrid antimicrobial polymer compositions for their physicalproperties on each respective type of glass substrate.

TABLE 9 Physical properties of antimicrobial-coated SCT glasssubstrates. “NR” denotes that the specified data were not collected. Alldata reported in the table are the average of ten independentdeterminations of the physical characteristic for each coupon of coatedglass. The data for Example 86 is the average (and standard deviation)for ten independent determinations of the physical characteristic forten separate coupons of glass that were coated on separate days with thesame working solution of AEM5700. Comparative examples, which do notcomprise an organosilane pendant group, are designated with the notation“comp.”. Coated Substrate Contact Scratch % Ref 20° 60° (Example No.)Angle Test % T Haze Clarity Haze gloss gloss 40 89.56 NR 91.20 8.7089.60 475.00 70.20 81.50 41 58.85 NR 92.00 6.30 89.80 413.00 73.00 83.6042 88.45 NR 91.80 5.80 88.50 431.00 75.50 85.50 43 comp. 108.25 NR 91.808.90 88.50 418.70 66.80 77.80 44 87.54 Pencil #7 91.00 7.44 88.97 454.0076.90 83.90 45 comp. 85.46 Pencil #7 91.00 6.57 87.70 441.00 80.17 86.0046 84.85 Pencil #7 90.77 6.73 87.03 426.00 80.57 86.03 47 comp. 80.72Pencil #7 90.97 6.68 87.27 451.00 79.03 85.10 48 comp. 72.06 Pencil #790.87 7.06 88.60 440.00 78.10 85.90 49 comp. 76.59 Pencil #7 90.93 7.5188.47 446.00 76.30 82.80 50 comp. 53.17 Pencil #7 91.73 7.56 88.23439.67 71.87 83.33 51 comp. 67.11 Pencil #6 91.77 7.28 88.17 429.6771.97 83.80 52 comp. 53.04 Pencil #6 91.73 8.29 89.33 423.67 68.07 77.6753 comp. 53.34 Pencil #6 91.77 7.83 88.20 433.67 66.13 74.53 54 comp.49.67 Pencil #6 91.63 7.66 88.90 430.33 71.90 81.47 55 comp. 49.24Pencil #7 91.60 8.08 89.13 432.00 71.57 79.03 56 comp. 58.68 Pencil #791.73 6.71 89.33 437.33 71.90 83.93 57 comp. 58.68 Pencil #7 91.77 6.3591.03 401.33 78.80 86.73 58 comp. 58.84 Pencil #8 91.57 12.57 89.37393.00 66.03 69.83 59 67.26 Pencil #7 91.30 10.08 89.53 416.33 70.8078.37 60 63.31 Pencil #7 91.50 9.26 89.63 423.00 71.13 80.17 61 67.98Pencil #6 91.80 6.62 89.57 435.33 73.87 84.40 62 72.61 Pencil #7 91.806.41 89.80 436.67 74.50 85.03 63 85.00 NR 90.80 6.98 89.30 477.00 72.3087.80 64 75.00 NR 91.90 5.80 87.80 440.00 74.50 85.80 65 89.00 NR 91.906.10 89.50 418.00 73.10 84.60 66 comp. 81.00 NR 91.80 6.80 89.20 422.0070.80 83.80 67 88.16 Pencil #7 91.10 6.76 87.80 460.00 77.97 84.93 68comp. 88.24 Pencil #7 90.90 7.39 88.90 455.00 78.87 85.73 69 86.81Pencil #7 91.03 7.04 87.60 420.00 79.03 86.70 70 comp. 85.48 Pencil #790.97 7.56 88.70 453.00 75.30 83.53 71 comp. 75.26 Pencil #7 90.87 7.0888.10 438.00 78.10 85.23 72 comp. 81.08 Pencil #7 90.97 8.31 88.80451.00 76.27 82.17 73 comp. 67.17 Pencil #7 91.57 7.68 89.57 421.0071.17 80.47 74 comp. 77.47 Pencil #8 91.70 7.03 89.43 432.00 76.27 87.6775 comp. 65.68 Pencil #6 91.63 7.28 88.20 434.33 76.83 86.70 76 comp.67.11 Pencil #7 91.80 7.49 88.50 463.00 73.60 84.30 77 comp. 66.72Pencil #6 91.63 8.36 89.17 437.33 74.17 84.50 78 comp. 71.04 Pencil #791.33 7.95 88.57 439.67 75.07 86.13 79 comp. 64.77 Pencil #7 91.77 7.3589.63 428.00 75.43 86.13 80 comp. 75.25 Pencil #7 91.53 6.74 90.00435.00 78.50 88.27 81 comp. 70.76 Pencil #7 91.70 8.95 89.50 407.6770.27 76.57 82 62.54 Pencil #5 91.60 9.10 90.20 413.33 70.90 76.77 8367.52 Pencil #6 91.53 8.20 90.50 404.33 72.13 79.93 84 69.72 Pencil #691.90 6.29 90.53 418.33 75.60 85.07 85 69.79 Pencil #6 91.87 6.40 90.73417.67 75.37 84.50 86 comp. 81.02 ± 10.50 Pencil #7 91.63 ± 0.35 7.00 ±0.93 89.20 ± 0.60 431.40 ± 19.40 74.70 ± 2.96 84.60 ± 2.77

TABLE 10 Physical properties of antimicrobial-coated DST glasssubstrates. All data reported in the table are the average of tenindependent determinations of the physical characteristic for eachcoupon of coated glass. The data for Example 133 is the average (andstandard deviation) for ten independent determinations of the physicalcharacteristic for ten separate coupons of glass that were coated onseparate days with the same working solution of AEM5700. Comparativeexamples, which do not comprise an organosilane pendant group, aredesignated with the notation “comp.”. Scratch Test Coated with hardnessSubstrate Contact pens loaded % Ref 20° 60° (Example No.) Angle 1000 g %T Haze Clarity Haze gloss gloss 87 85.21 pencil 6 visible 92.3 4.79 78.3564 22.4 75.4 88 67.42 pencil 6 visible 92.3 4.52 77.9 578 22 75.4 8989.7 pencil 7 visible 92.4 4.55 77.47 571 21 74.4 90 comp. 83.79 pencil8 visible 92 10.77 77.3 513 17.5 58.23 91 94.09 Pencil #5 visible 91.910.45 72.9 487 14.7 55.4 92 comp. 82.26 Pencil #5 visible 92.2 5.6 74.1533.7 17.1 68.2 93 88.13 Pencil #5 visible 92.1 5.8 73.2 532 16.7 67.694 comp. 76.39 Pencil #4 visible 92.2 5.8 73 529.7 16.7 67.7 95 comp.79.14 Pencil #4 visible 92 6.1 72.9 528.7 16.7 67.3 96 comp. 83.58Pencil #4 visible 91.8 9.8 72.6 493.3 14.8 58.1 97 comp. 58.81 Pencil#7-Visible 92.30 5.91 76.90 547.33 19.13 70.80 98 comp. 67.00 Pencil#7-Visible 92.33 5.66 77.63 560.00 20.17 73.20 99 comp. 71.33 Pencil#8-Visible 92.43 6.87 78.73 508.33 17.90 68.43 100 comp. 58.56 Pencil #7visible 92.17 6.83 71.60 520.67 15.70 65.97 101 comp. 64.58 Pencil#8-Visible 92.30 6.77 74.83 489.33 17.47 65.63 102 comp. 60.30 Pencil #7visible 92.13 7.72 72.73 477.33 14.67 62.37 103 comp. 54.51 Pencil #7visible 92.10 6.17 74.90 551.33 18.70 69.77 104 comp. 62.70 Pencil #7visible 92.13 6.23 74.67 549.67 18.27 68.67 105 comp. 67.55 Pencil#8-Visible 91.67 15.00 72.47 486.33 15.13 51.60 106 61.35 Pencil #6visible 92.47 9.31 74.57 506.00 16.43 59.03 107 54.38 Pencil #6 visible92.50 6.69 76.95 537.50 18.00 66.55 108 44.63 Pencil #7 visible 92.675.51 75.70 536.67 17.53 68.33 109 58.18 Pencil #7 visible 92.53 8.1274.73 503.00 15.60 58.90 110 88.88 pencil 7 visible 92.1 10.33 67.3 47013.1 56 111 64.24 pencil 7 visible 92.3 5.98 69.7 518 15.2 65.3 11290.44 pencil 7 visible 92.3 5.93 70.1 520 15.6 65.9 113 comp. 86.34pencil 7 visible 92 9.67 70.6 500 14.8 60.3 114 94.46 Pencil #4 visible92.10 6.92 72.97 516.00 16.10 63.80 115 comp. 89.31 Pencil #4 visible92.10 6.17 72.93 522.67 16.23 66.30 116 89.77 Pencil #4 visible 92.105.94 71.40 523.67 15.87 66.37 117 comp. 84.88 Pencil #6 visible 92.076.19 70.37 513.00 15.20 65.07 118 comp. 82.01 Pencil #6 visible 92.036.16 71.83 520.67 16.00 66.67 119 comp. 86.04 Pencil #7 visible 92.006.62 76.13 541.00 17.80 67.07 120 comp. 69.72 Pencil #6-Visible 92.406.17 78.50 536.00 20.90 71.13 121 comp. 94.94 Pencil #5-Visible 92.634.49 77.37 558.67 21.87 74.53 122 comp. 96.19 Pencil #5-Visible 92.475.22 78.47 539.00 20.07 71.23 123 comp. 69.78 Pencil #6 visible 92.135.22 74.20 540.33 18.40 69.53 124 comp. 66.84 Pencil #7 visible 92.105.37 73.67 547.33 18.20 69.20 125 comp. 67.10 Pencil #7 visible 91.975.35 73.77 551.00 18.03 69.70 126 comp. 68.12 Pencil #7 visible 92.005.62 74.27 546.00 17.50 68.17 127 comp. 66.43 Pencil #7 visible 92.035.52 74.13 554.33 18.77 70.43 128 comp. 70.32 Pencil #7 visible 91.976.45 74.10 549.33 18.17 66.80 129 56.55 Pencil #7 visible 92.40 10.1775.27 516.00 16.67 59.87 130 52.83 Pencil #7 visible 92.43 8.36 74.90512.67 16.27 62.00 131 73.09 Pencil #6 visible 92.57 7.02 72.87 514.6715.37 62.03 132 65.94 Pencil #6 visible 92.57 6.73 71.83 526.33 15.9063.97 133 comp. 75.29 ± 18.64 Pencil #6 visible 92.32 ± 0.21 5.43 ± 0.4873.30 ± 2.87 537.80 ± 19.25 17.23 ± 1.78 68.48 ± 3.08

TABLE 11 Physical properties of antimicrobial-coated PCT glasssubstrates. All data reported in the table are the average oftenindependent determinations of the physical characteristic for eachcoupon of coated glass. The data for Examples 149 and 150 are theaverages (and standard deviations) for ten independent determinations ofthe physical characteristic for two separate coupons of glass that werecoated on separate days with the same working solution of AEM5700.Comparative examples, which do not comprise an organosilane pendantgroup, are designated with the notation “comp.”. Coated SubstrateAdvancing (Example Contact Eraser % Ref 20° 60° No.) Angle Rub Test % THaze Clarity Haze gloss gloss 134 98.38 18.50 93.60 5.75 91.43 468.3362.67 78.07 135 comp. 92.69 27.00 93.27 5.74 91.23 482.67 67.10 80.10136 82.05 10.00 93.57 6.33 90.93 465.67 59.87 74.90 137 comp. 77.6516.00 93.1 7.3 90.3 483.3 61.2 73.6 138 comp. 94.60 15.50 93.6 5.0 92.7461.3 67.1 81.8 139 88.72 13.50 93.2 5.4 92.7 471.7 70.6 82.7 140 comp.86.10 12.50 93.5 5.9 92.0 440.0 64.9 79.0 141 80.52 15.50 93.2 5.2 91.8477.3 68.9 82.7 142 comp. 86.89 17.50 93.6 5.3 93.2 453.0 68.7 82.7 143comp. 80.81 15.50 93.2 5.4 92.2 475.7 71.2 83.7 144 94.09 20.00 93.535.69 93.17 446.33 66.90 80.93 145 comp. 93.71 37.50 93.20 5.17 91.77483.00 70.40 83.73 146 87.01 15.00 92.90 4.34 90.47 518.67 68.17 79.60147 comp. 85.82 26.50 93.20 5.47 92.23 473.33 69.90 82.37 148 comp.95.14 27.50 93.50 4.79 92.30 471.67 67.73 84.03 150 92.55 36.50 93.076.35 90.97 475.67 65.53 77.90 151 comp. 86.94 15.50 92.9 4.9 88.4 526.762.6 74.7 152 84.87 22.50 93.1 6.8 90.3 478.0 63.4 75.5 153 comp. 84.9615.00 92.9 4.6 88.2 529.7 62.9 75.1 154 comp. 87.33 21.50 93.2 6.7 91.3468.0 65.5 78.1 149 88.34 ± 1.39 25.50 ± 4.24 93.2 ± 0.6 5.0 ± 0.1 90.6± 1.7 526.05.2± 64.2 ± 0.9 78.1 ± 1.1 155 90.62 ± 2.43 36.00 ± 6.36 93.3± 0.0 4.8 ± 0.1 92.2 ± 1.3 452.4 ± 22.1 71.9 ± 1.3 85.6 ± 2.0

Example 157 Antimicrobial Activity Testing for AntimicrobialPolymer-Coated Glass Substrates and Hybrid Antimicrobial Polymer-CoatedGlass Substrates

Antimicrobial activity of the coated glass substrates was tested usingthree standard methods. The ASTM 2149 test method (ASTM International;West Conshohocken, Pa.) was used to evaluate the effectiveness of thenon-leaching antimicrobial polymer-coated surfaces of the glass coupons.Overnight cultures of Staphylococcus aureus (ATCC 6538) andStaphylococcus. epidermidis (ATCC 12228) were diluted in phosphatebuffer to a concentration of approximately 1×10⁶ CFU/ml. A 1×1-inch(2.54 cm×2.54 cm) square of glass sample was placed into a tubecontaining 50 ml of dilute bacterial suspensions. The samples wereincubated with constant agitation for 24 hours at 28+/−1° C. Immediatelyafter the samples were placed into the tubes (T=0 hr) and after 24 hours(T=24 hr), a small aliquot of the suspension was serially-diluted andthe diluted samples were inoculated onto Petrifilm Aerobic Count (AC)Plates (3M Company, St. Paul, Minn.) according to the manufacturer'sinstructions. The plates were incubated for 48 hours at 35° C.+1° C.Bacterial colonies from appropriate dilution were counted according tothe manufacturer's instructions and recorded as colony-forming units(CFU) per ml.

The JIS Z 2801 test method (Japan Industrial Standards; JapaneseStandards Association; Tokyo, JP) was used to evaluate the antibacterialactivity of antibacterial polymer-coated glass substrates. The bacterialinoculum was prepared in a solution of 1 part Nutrient Broth (NB) and499 parts phosphate buffer. A portion of the inoculum was used todetermine the number of viable bacteria in the inoculum. Another portionof the bacterial suspension (150 μL) was placed onto the surface of theglass sample and the inoculated glass sample was incubated for thespecified contact time at 28+/−1° C. (see FIG. 5). After incubation, theglass sample was placed into 20 ml of D/E Neutralizing Broth. The numberof surviving bacteria in the Neutralizing broth was determined byinoculating the broth onto nutrient agar using a Spiral Plater WASP II,DW Scientific, Shipley, West Yorkshire, UK, incubating the plates for 24hours at 35° C.+1° C. and counting the colonies using a colony reader(ProtoCol colony Counter; Microbiology International; Frederick, Md.).FIG. 6 shows a comparison of the results from 5 different coated samplesthat were tested using the ASTM 2149 test method and the JIS Z 2801 testmethod. This experimental data from the JIS test method showed a greaterthan 3-log reduction of the microorganisms after a two hour contact timewith the antimicrobial polymer-treated glass samples. In thisexperiment, the control was SCT glass that was not treated with anantimicrobial polymer.

Test method ASTM E2180-01 was designed to evaluate quantitatively theantimicrobial effectiveness of antimicrobial coatings on the coatedsurfaces. Overnight cultures of Staphylococcus aureus (ATCC 6538) wereused to inoculate the agar slurry, which was applied to theantimicrobial polymer-coated surface of the glass samples. Themicroorganisms were recovered from inoculated agar slurry usingDey/Engley (D/E) Neutralizing Broth. Bacterial plate counts wereperformed using 3M Petrifilm Aerobic Count (AC) Plates (3M Company, St.Paul, Minn., USA) according to the manufacturer's instructions. Thecolony counts were recorded as colony-forming unit (CFU) per cm². Thedifference between bacterial count in a slurry when the inoculum isimmediately applied to the surface (T=0 hr) and the bacterial count inthe slurry after 24 hours of contact with the antimicrobial surface isrecorded as the log 10 reduction. The polymer-treated glass samples werecompared to an untreated sample of PET film (Acrylate-primer coatedpolyethylene terephthalate film, 4 mil (0.10 mm) thick, obtained fromMitsubishi Polyester Film, Greer, S.C.). The results (not shown)indicate that each of the antimicrobial polymer-treated glass sampleshad a log 10 reduction of about 0.5 to about 0.8 using this test method.

Comparative Example 158 Synthesis of Comparative Antimicrobial Polymer

A comparative antimicrobial polymer was synthesized according to ExampleNo. 2 of PCT Patent Application Publication No. WO2010/036465. Thepolymer was diluted in IPA to 5 wt % and was coated ontoconductively-coated glass (part number 29617), obtained from PilkingtonNorth America, Inc. (Toledo, Ohio), as described in Examples 40-62above. The surface hydrophobicity of the resulting coated substrate wascompared to the coated sample of Example 65 by measuring the contactangle of a drop of deionized water on each coated substrate using ASTMtest method D7334.7606. The results are shown in Table 12. The resultsindicate that the antimicrobial polymer of Example 65 was morehydrophobic than the polymer of comparative Example 158.

TABLE 12 Comparison of surface hydrophobicity of coated substrates.Advancing Coated Substrate Contact Angle Comparative Example 158 30.6Example 65 96.12

Examples 159-162 Synthesis of Comparative Antimicrobial Polymer

Samples of SCT glass were prepared and coated using the proceduresdescribed in Examples 40-62. Samples of PCT glass were prepared andcoated using the procedures described in Examples 134-143. Therespective coating formulations are listed in Table 13. A1120(N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane) was added to thecoating solutions as an adhesion-promoting reagent. Tin-octoate wasadded to the coating solutions as a catalyst to promote cross-linkingreactions. After applying the coating formulations to the glass andallowing evaporation of the solvent, the coated substrates in Examples159, 161, and 162 were placed in a convection oven (138° C.) for 4minutes and then cooled to room temperature. After applying the coatingformulations to the glass and allowing evaporation of the solvent, thecoated substrates in Example 160 was placed in a convection oven (120°C.) for 3 minutes and then cooled to room temperature. After cooling,all substrates were immediately washed in a Billco washer as describedin Examples 40-62.

TABLE 13 Coating solutions for Examples 159-162. Example SubstrateCoating Formulation 159 SCT A 1:1 blend of 3 Wt % (in IPA) AEM5700 and 5Wt % (in IPA) of the polymer of Example 6, to which 2 Wt % tin-octoateand 0.04 Wt % A1120 were added. 160 PCT A 1:1 blend of 3 Wt % (in IPA)AEM5700 and 5 Wt % (in IPA) of the polymer of Example 6, to which 2 Wt %tin-octoate and 0.04 Wt % A1120 were added. 161 SCT 5 Wt % (in IPA) ofthe polymer of Example 6, to which 2 Wt % tin-octoate was added 162 PCT5 Wt % (in IPA) of the polymer of Example 6, to which 2 Wt % tin-octoatewas added

The samples were tested for antimicrobial activity using the JIS Z 2801test procedure described in Example 157. Uncoated samples of each typeof glass were used as controls. The bacterial inoculum was prepared in asolution of 1 part Nutrient Broth (NB) and 499 parts phosphate buffer. Aportion of the inoculum was used to determine the number of viablebacteria in the inoculum. Another portion of the bacterial suspension(150 μL) was placed onto the surface of the glass sample and theinoculated glass sample was incubated for the specified contact time at28°±1° C. After incubation, the glass sample was placed into 20 ml ofD/E Neutralizing Broth. The number of surviving bacteria in theNeutralizing broth was determined by inoculating the broth onto nutrientagar using a Spiral Plater WASP, incubating the plates for 24 hours at35° C.+1° C. and counting the colonies using a colony reader (ProtoColcolony Counter; Microbiology International; Frederick, Md.). The resultsare shown in Tables 14 and 15, which show data from experimentsconducted on separate days.

Comparative Examples 163-164 Synthesis of Comparative AntimicrobialPolymer

Samples of SCT glass were prepared and coated using the proceduresdescribed in Examples 40-62. Samples of PCT glass were prepared andcoated using the procedures described in Examples 134-143. Therespective coating formulations are listed in Table 14. A1120(N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane) was added to thecoating solutions as an adhesion-promoting reagent. Tin-octoate wasadded to the coating solutions as a catalyst to promote cross-linkingreactions. After applying the coating formulations to the glass andallowing evaporation of the solvent, the coated substrates inComparative Example 161 was placed in a convection oven (138° C.) for 4minutes and then cooled to room temperature. After applying the coatingformulations to the glass and allowing evaporation of the solvent, thecoated substrates in Comparative Example 162 was placed in a convectionoven (120° C.) for 3 minutes and then cooled to room temperature. Aftercooling, all substrates were immediately washed in a Billco washer asdescribed in Examples 40-62.

TABLE 14 Coating solutions for Comparative Example 163-164. ComparativeExample Substrate Coating Formulation 163 SCT A mixture of 3 Wt %AEM5700 in IPA with 2 Wt % tin-octoate and 0.04% A1120. 164 PCT Amixture of 3 Wt % AEM5700 in IPA with 2 Wt % tin-octoate and 0.04%A1120.

The samples were tested for antimicrobial activity using the JIS Z 2801test procedure described for Examples 159-160. Uncoated samples of eachtype of glass were used as controls. The results are shown in Tables 15and 16, which show data from experiments conducted on separate days.

TABLE 15 Tests for antibacterial properties of coated-glass samples.Bacterial suspensions were tested for viable cells after 15 minutes and2 hours contact time with the coated glass surfaces, respectively. Allresults are the average of three samples tested for each type. Log₁₀Log₁₀ Reduction Reduction of viable of viable Log₁₀ Log₁₀ bacteriabacteria cfu cfu after 15-min. after 2-hour Sample (15-min) (2 hr)contact time contact time Control (SCT glass) 5.56 5.58 0 0 Control (PCTglass) 5.53 5.65 0 0 Example 159 3.95 1.48 1.61 4.1 Example 160 3.441.05 2.09 4.6 Comp. Example 163 5.37 4.27 0.19 1.31 Comp. Example 1645.42 4.12 0.11 1.53 cfu = colony-forming unit.

TABLE 16 Tests for antibacterial properties of coated-glass samples.Bacterial suspensions were tested for viable cells after 15 minutes and2 hours contact time with the coated glass surfaces, respectively. Allresults are the average of three samples tested for each type. Log₁₀Log₁₀ Reduction Reduction of viable of viable Log₁₀ Log₁₀ bacteriabacteria cfu cfu after 15-min. after 2-hour Sample (15-min) (2 hr)contact time contact time Control (SCT glass) 5.51 5.64 0 0 Control (PCTglass) 5.53 5.65 0 0 Example 159 3.38 0.90 2.13 4.61 Example 160 4.321.07 1.2 4.43 Example 161 4.35 0.99 1.16 4.52 Example 162 4.48 1.45 1.044.05 Comp. Example 163 5.14 3.69 0.37 1.82 Comp. Example 164 5.37 4.210.15 1.29 cfu = colony-forming unit.

The present invention has now been described with reference to severalspecific embodiments foreseen by the inventor for which enablingdescriptions are available. Insubstantial modifications of theinvention, including modifications not presently foreseen, maynonetheless constitute equivalents thereto. Thus, the scope of thepresent invention should not be limited by the details and structuresdescribed herein, but rather solely by the following claims, andequivalents thereto.

What is claimed is:
 1. An article, comprising: a touch-sensitivesubstrate comprising a surface; a first layer coated on the surface, thefirst layer comprising an adhesion-promoting reagent; and a second layercoated on the first layer, the second layer comprising an organicpolymer having a plurality of pendant groups comprising a first pendantgroup comprising a first quaternary ammonium component; a second pendantgroup comprising a nonpolar component; a third pendant group comprisinga first organosilane component.
 2. The article of claim 1, wherein theadhesion-promoting reagent is selected from the group consisting of3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, and3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-(2-aminoethyl)aminopropyltrimethoxysilane,(aminoethylaminomethyl)phenethyltrimethoxysilane,(aminoethylaminomethyl)phenethyltriethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,bis-(γ-triethoxysilylpropyl)amine,N-(2-aminoethyl)-3-aminopropyltributoxysilane,6-(aminohexylaminopropyl)trimethoxysilane, 4-aminobutyltrimethoxysilane,4-aminobutyltriethoxysilane, p-(2-aminoethyl)phenyltrimethoxysilane,3-aminopropyltris(methoxyethoxyethoxy)silane,3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomersthereof, methyltriethoxysilane and oligomers thereof, an oligomericaminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane,3-aminopropyldimethylmethoxysilane, and3-aminopropyldimethylethoxysilane.
 3. An article made by the process of:forming a first composition of an organic polymer in organic solvent,the polymer having a plurality of pendant groups comprising, a firstpendant group comprising a first quaternary ammonium component, a secondpendant group comprising a nonpolar component, and a third pendant groupcomprising a first organosilane component; mixing a second quaternaryammonium component with the first composition to form a first mixture;and contacting the first mixture with a substrate under conditionssuitable to form covalent linkages between the organic polymer, thesubstrate, and the second quaternary ammonium component.